UNITED STATES TARIFF COMMISSION
SYNTHETIC RESINS
AND THEIR RAW MATERIALS
REPORT No. 131
SECOND SERIES
[Illustration]
RECENT REPORTS OF THE UNITED STATES TARIFF COMMISSION
REPORTS TO THE PRESIDENT
_Under the Rate Adjustment Provisions (Sec. 336) of the
Tariff Act of 1930_
Dressed or Dyed Furs, Report No. 122, Second Series, 1937 $0.05
Slide Fasteners (Zippers), Report No. 113, Second Series, 1936 .10
_Under the Unfair Practices Provisions (Sec. 337) of the
Tariff Act of 1930_
Coilable Metal Rules, Report No. 106, Second Series, 1936 .05
REPORTS TO THE UNITED STATES SENATE
_Under the General Powers Provision (Sec. 332) of the
Tariff Act of 1930_
Nets and Netting and Other Fishing Gear, Report No. 117, Second
Series, 1937 .10
Salmon and Other Fish, Report No. 121, Second Series, 1937 .15
Subsidies and Bounties to Fisheries Enterprises by Foreign
Countries, Report No. 116, Second Series, 1936 .15
Tuna Fish, Report No. 109, Second Series, 1936 .10
Wood Pulp and Pulpwood, Report No. 126, Second Series, 1938 .30
OTHER REPORTS UNDER THE GENERAL POWERS PROVISION OF THE
TARIFF ACT OF 1930
Dominion and Colonial Statistics, Report No. 127, Second
Series, 1938 .10
Dyes and Other Synthetic Organic Chemicals in the United
States, 1937, Report No. 132, Second Series, 1938 .10
Extent of Equal Tariff Treatment in Foreign Countries,
Report No. 119, Second Series, 1937 .15
The Mica Industry, Report No. 130, Second Series, 1938 .25
Chemical Nitrogen, Report No. 114, Second Series, 1937 .25
Flat Glass and Related Glass Products, Report No. 123,
Second Series, 1937 .35
Iron and Steel, Report No. 128, Second Series, 1938 .60
Cutlery Products, Report No. 129, Second Series, 1937 .15
TRADE AGREEMENTS INFORMATION
Trade Agreement With Canada (a summary of the provisions of
this agreement), Report No. 111, Second Series, 1936 .15
_Miscellaneous Reports_
Changes in Import Duties Since the Passage of the Tariff Act
of 1930, Miscellaneous Series, 1937 .10
Rules of Practice and Procedure (Sixth Revision) and Laws
Relating to the United States Tariff Commission, Miscellaneous
Series, 1938 .10
For sale by the Superintendent of Documents, Government Printing Office,
Washington, D. C., at the prices indicated
UNITED STATES TARIFF COMMISSION
Washington
ERRATA
Since publication of the report on Synthetic Resins the Commission’s
attention has been called to certain necessary corrections.
Page 37—2d line under heading “Production in the United States”
_Strike out_ “The Resinous Products and Chemical Co., Inc.,” and
_insert_ “Rohm and Haas,”
Page 154—Last item under “Vinyl Resins”
_Transfer_ the name of E. I. du Pont de Nemours and Co., Wilmington,
Del. to line below so that it will not be opposite a trade name. This
company manufactures Vinyl Resins but not “Koroseal”.
December 1938
Transcriber’s Note: The errata have been corrected for this e-text,
together with a number of sundry typos.
UNITED STATES TARIFF COMMISSION
SYNTHETIC RESINS
AND THEIR RAW MATERIALS
A SURVEY OF THE TYPES AND USES OF SYNTHETIC
RESINS, THE ORGANIZATION OF THE INDUSTRY,
AND THE TRADE IN RESINS AND RAW
MATERIALS, WITH PARTICULAR
REFERENCE TO FACTORS
ESSENTIAL TO TARIFF
CONSIDERATION
UNDER THE GENERAL PROVISIONS OF SECTION 332, TITLE III,
PART II, TARIFF ACT OF 1930
REPORT No. 131
SECOND SERIES
[Illustration]
UNITED STATES
GOVERNMENT PRINTING OFFICE
WASHINGTON: 1938
For sale by the Superintendent of Documents, Washington, D. C.
Price 25 cents
UNITED STATES TARIFF COMMISSION
_RAYMOND B. STEVENS, Chairman_
_HENRY F. GRADY, Vice Chairman_
_EDGAR B. BROSSARD_
_OSCAR B. RYDER_
_E. DANA DURAND_
_A. MANUEL FOX_
_SIDNEY MORGAN, Secretary_
Address All Communications
UNITED STATES TARIFF COMMISSION
WASHINGTON, D. C.
TABLE OF CONTENTS
Page
Acknowledgment XI
1. Introduction 1
Scope and purpose 2
Fundamental definitions 2
Tariff history 3
Broadening use of synthetic resins 4
Relation of synthetic resins to their raw materials 5
Sources of information 7
2. Summary:
Growth of the industry 7
Raw materials 8
Resins 9
The industry abroad 10
International trade 10
3. Tar-acid resins 11
The three stages of a tar-acid resin 13
Classification of tar-acid resins 13
Processes of resin manufacture 14
Production in the United States 15
Imports into the United States 16
Exports from the United States 17
Tar-acid resins for molding:
Molding powders and pellets 18
The molding of tar-acid resins 19
Production of tar-acid molding resins 19
Cast phenolic resins:
Process of manufacture 20
Uses 20
Patents and licensing 21
Production of cast phenolic resins 21
Imports and exports 21
Tar-acid resins for laminating 21
Uses of tar-acid resin laminated products 22
Production of tar-acid resins for laminating 23
Imports into the United States 24
Exports from the United States 24
Tar-acid resins for surface coatings:
Types of resin used and the resultant coatings 24
Production in the United States 25
Imports into and exports from the United States 25
Tar-acid resins in adhesives 25
Tar-acid resins for other uses 26
4. Alkyd resins:
Description and uses 26
Development and patents 27
Classification of alkyd resins:
Unmodified drying alkyd resins 28
Drying alkyd resins, modified with natural materials 29
Drying alkyd resins, modified with other synthetic resins 29
Drying alkyd resins, modified with other synthetic resins
and oil extended 29
Semidrying alkyd resins 29
Nondrying alkyd resins 30
Miscellaneous modified alkyd resins 30
Alkyd resins in water dispersion 30
Alkyd resins in molding compositions and other uses 30
Pigments and solvents in alkyd resins 31
Production in the United States 31
Imports into and exports from the United States 32
5. Urea resins:
Description and uses 32
Production in the United States 34
United States imports and exports 35
6. Acrylate resins:
Properties and uses 35
Production in the United States 37
Imports into and exports from the United States 38
7. Coumarone and indene resins:
Description and uses 38
Production in the United States 39
Imports into and exports from the United States 39
8. Petroleum resins:
Properties and uses 39
Production 41
Imports and exports 41
9. Polystyrene resins:
Properties and uses 41
Production in the United States 42
Imports into and exports from the United States 42
10. Vinyl resins 43
Description and uses:
Polyvinyl acetate resins 44
Copolymers of vinyl acetate and vinyl chloride 46
Polyvinyl chloride resins 47
Polyvinyl chloroacetate resins 47
Divinyl acetylene and synthetic rubber 47
Production in the United States 48
Imports into the United States 48
Exports from the United States 50
11. Other synthetic resins:
Adipic acid resins 50
Aniline resins 50
Citric acid resins 50
Diphenyl resins 51
Furfural resins 51
Resins from sugar 51
Sulphonamide resins 51
12. The organization of the synthetic resin industry:
Horizontal relationships between resin producers 52
Vertical relationships between resin producers:
Tar-acid resins for molding 53
Tar-acid resins for laminating 54
Cast phenolic resins 54
Tar-acid resins for coatings 55
Tar-acid resins for miscellaneous uses 55
Alkyd resins made from phthalic anhydride 55
Alkyd resins made from maleic anhydride 55
Urea resins for molding 56
Urea resins for other uses 56
Coumarone and indene resins 56
Other resins 56
Relationship of the resin industry to other industries:
The chemical industry 56
The surface-coating industry 57
The electric industry 57
The auto industry 57
13. The United States tariff and international trade in synthetic
resins 58
Rapid expansion in home markets 59
The effect of patents on international trade 59
The United States tariff on resins and resin products:
Synthetic resins 60
Articles made of synthetic resin 61
14. Synthetic resin prices, properties, and uses:
Synthetic resins as substitutes 62
Motives for substitution 63
Materials displaced by synthetic resins 63
Competition between synthetic resins 63
Resins classified by cost 64
The physical properties of a resin and its uses 65
15. Synthetic resins in other countries:
Germany:
Production 75
Tar-acid resins 75
Alkyd resins 76
Urea resins 76
Polystyrene and vinyl resins 76
Uses of synthetic resins 76
Organization 77
Foreign trade 77
Great Britain:
Production 78
Tar-acid resins 79
Urea resins 79
Acrylate resins 79
Aniline resin 79
Organization 79
Foreign trade 80
France:
Producers 80
Foreign trade 81
Czechoslovakia 82
Italy 82
Japan 83
Production 83
Canada 84
Union of Soviet Socialist Republics 85
Netherlands 85
Denmark 86
Poland 86
16. Raw materials for alkyd resins 86
Naphthalene:
Recovery of naphthalene 87
Description and uses 87
United States production 88
Organization of the industry 89
Trend of production 89
World production 90
Germany 91
Great Britain 92
Belgium 93
Czechoslovakia 93
France 94
Poland 94
Netherlands 94
Canada 94
Union of Soviet Socialist Republics 94
Japan 94
United States imports:
Rates of duty 95
Import statistics 96
United States exports 98
Competitive conditions 98
Phthalic anhydride:
Description and uses 98
United States production 100
Production in other countries 101
United States foreign trade 101
Competitive conditions 101
Polybasic acids other than phthalic anhydride:
Maleic acid and anhydride 102
Malic acid and malomalic acid 102
Adipic acid 102
Succinic acid and anhydride 102
Fumaric acid 102
Glycerin:
Description and uses 103
United States production 103
Production in other countries 104
International trade 104
United States imports 105
United States exports 107
Competitive conditions 108
17. Raw materials for tar-acid resins:
The tar acids 109
Phenol:
Description and uses 110
United States production 111
Grades produced for resins 112
Producers 112
World production 113
United States imports:
Rates of duty 114
Import statistics 114
United States exports 116
Competitive conditions 116
The cresols, xylenols, and cresylic acid:
Description and uses:
The cresols 117
Metacresol 118
Orthocresol 118
Paracresol 118
Metaparacresol 118
Cresol 118
The xylenols 118
Other high-boiling tar acids 119
Cresylic acid 119
United States production:
The cresols 120
The xylenols 120
Other high-boiling tar acids 120
Cresylic acid 120
Foreign production 122
United States imports:
Rates of duty 124
Import statistics 125
United States exports 131
Competitive conditions 131
Synthetic tar acids other than phenol 132
Para tertiary amyl phenol 133
Para tertiary butyl phenol 133
Phenyl phenols 133
Resorcinol 133
Formaldehyde:
Description and uses 133
United States production 134
Production in other countries 134
United States imports and exports 134
Competitive conditions 135
Hexamethylenetetramine:
Description and uses 136
United States production 136
Production in other countries 136
United States imports and exports 136
Competitive conditions 137
Furfural 137
18. Raw materials for urea resins:
Urea 138
Thiourea 139
19. Raw materials for vinyl resins:
Description and uses 140
United States production 140
United States imports 141
Competitive conditions 141
APPENDIXES
Appendix A. Statistical tables on foreign trade in raw material
for synthetic resins 144
Appendix B. Trade names for synthetic resins made in the United
States 153
Appendix C. Trade names for synthetic resins made in Great Britain 155
Appendix D. Trade names for synthetic resins made in Germany 156
Appendix E. List of United States manufacturers of raw materials
for synthetic resins 158
Appendix F. Glossary 160
TABLES
No.
1. Synthetic resins: United States production and sales, 1921-37 8
2. Tar-acid resins: United States production and sales, by type
of raw material, 1933-37 14
3. Tar-acid resins: United States production and sales, 1927-37 15
4. Synthetic resins of coal-tar origin: United States imports for
consumption, 1919-37 16
5. Synthetic resins of coal-tar origin: United States imports for
consumption, by principal sources, in specified years 1929-37 17
6. Cast phenolic resins: United States production and sales,
1934-37 21
7. Alkyd resins from phthalic and maleic anhydride: United States
production and sales, 1933-37 31
8. Urea resins: United States production and sales, 1933-37 35
9. Resoglas and Trolitul: United States imports for consumption,
1933-37 43
10. Synthetic resins classified under paragraph 11: United States
imports for consumption, 1931-37 49
11. Vinyl acetate resins: United States imports for consumption,
1934-37 49
12. Mowilith resins: United States imports for consumption, 1932-37 49
13. Synthetic resins: United States production and imports, 1934-37 58
14. Comparison of the international trade of the United States in
synthetic resins and in certain raw materials for resins,
1934-37 58
15. Tariff classification and rates of duty in Tariff act of 1930
upon certain articles made of synthetic resin 61
16. Manufactured articles n. s. p. f. in which synthetic resin
is the chief binding agent: United States imports for
consumption, 1931-37 62
17. Synthetic resins and other plastics: Properties that affect
appearance 66
18. Synthetic resins and other plastics: Molding properties 68
19. Synthetic resins and other plastics: Strength properties 70
20. Synthetic resins and other plastics: Heat properties 71
21. Synthetic resins and other plastics: Electrical properties 72
22. Synthetic resins and other plastics: Specific gravity,
specific volume, and resistance to other substances 73
23. Synthetic resins: German exports, 1930-37 77
24. Synthetic resins: German exports, by countries, 1934-37 78
25. Synthetic resins: Production in Great Britain, 1934 and 35 78
26. Synthetic resins: Imports into the United Kingdom, 1930-36 80
27. Synthetic resins: Exports from the United Kingdom, 1930-36 80
28. Synthetic resins: French imports, by types, and countries,
1931 and 1933-37 81
29. Synthetic resins: French exports, 1931 and 1933-37 82
30. Manufactures of tar-acid resins: Production in Japan, 1929-35 84
31. Prices of gums and resins in the Netherlands, 1936 86
32. Synthetic resins: Netherland imports by countries 1931
and 1933-37 86
33. Crude naphthalene: United States production, 1918-37 88
34. Refined naphthalene: United States production and sales, 1917-37 89
35. Naphthalene (all grades): World production, by countries,
1933 and 1935 90
36. Naphthalene: German production, imports, exports, and apparent
consumption, 1928-37 92
37. Naphthalene: Production in Great Britain, in specified years 92
38. Naphthalene: Exports from the United Kingdom, 1928-36 93
39. Naphthalene: Belgian production, 1928-35 93
40. Naphthalene: Czechoslovak production, 1928-35 93
41. Crude naphthalene: Polish production, 1928-36 94
42. Naphthalene: Rates of duty upon imports into the United
States, 1916-38 95
43. Crude naphthalene (solidifying at less than 79° C.): United
States imports for consumption, 1919-37 96
44. Refined naphthalene (solidifying at or above 79° C.): United
States imports for consumption, 1919-37 96
45. Crude naphthalene (solidifying under 79° C.): United States
imports for consumption from principal sources, in specified
years 97
46. Crude naphthalene: United States production, imports, and
apparent consumption, in specified years 98
47. Phthalic anhydride: United States production and sales, 1917-37 100
48. Glycerin: United States production, 1919-37 103
49. Glycerin: United States production for sale, 1919-35 104
50. Glycerin: Imports and exports of principal countries, 1931
and 1933-37 105
51. Glycerin: United States imports for consumption, 1919-20
and 1923-37 106
52. Crude glycerin: United States imports for consumption from
Cuba, 1919-37 107
53. Crude glycerin: United States imports for consumption from
Philippine Islands, 1925-37 107
54. Glycerin: United States exports, 1919-37 108
55. Refined glycerin: United States production, imports, exports,
and apparent consumption, in specified years 108
56. Tar acids: Commercial and chemical names, boiling points, and
average percent in coal tar 109
57. Tar acids available in coal tar produced and distilled in 1936 110
58. Phenol: Estimated consumption by industries, 1936-37 111
59. Phenol: United States production and sales, in specified
years, 1918-37 112
60. Phenol: Estimated annual production, by countries, 1933-35 113
61. Phenol: Rates of duty upon imports into the United States,
1916-37 114
62. Phenol: United States imports for consumption, 1910-37 115
63. All distillates of tar yielding below 190° C., an amount of
tar acids equal to or more than 5 percent: United States
imports for consumption, 1918-37 115
64. Phenol: United States exports, 1918-24 116
65. Phenol: United States exports, 1934-36 116
66. Phenol: United States production, imports, exports, and
apparent consumption, in specified years, 1918-37 117
67. Meta, ortho, and para cresols: United States production and
sales, 1934 120
68. Refined cresylic acid: United States production and sales,
1929-37 121
69. Cresol: German production, in specified years 122
70. Cresol: German imports and exports in specified years 122
71. Cresol: Production in Czechoslovakia in specified years 123
72. Cresylic acid: British exports, by countries, 1933-37 123
73. The cresols: Rates of duty upon United States imports, 1916-37 124
74. Cresylic acid: Rates of duty upon United States imports,
1916-37 125
75. Metacresol, orthocresol, and paracresol, 90 percent or
more pure: United States imports for consumption, 1920
and 1923-37 125
76. Metacresol: United States imports for consumption by principal
sources, in specified years 126
77. Orthocresol: United States imports for consumption by principal
sources, in specified years 127
78. Paracresol: United States imports for consumption by principal
sources, in specified years 128
79. Crude cresylic acid: United States imports for consumption,
1924-37 129
80. Refined cresylic acid: United States imports for consumption,
in specified years, 1919-37 129
81. Crude cresylic acid: United States imports for consumption by
principal sources, in specified years, 1929-37 130
82. Refined cresylic acid: United States imports for consumption
by principal countries, in specified years 130
83. The cresols: Comparison of production and imports, 1934 132
84. Formaldehyde: United States production and sales, in specified
years 134
85. Formaldehyde: United States exports to principal markets, in
specified years 135
86. Hexamethylenetetramine: United States production and sales,
1923 and 1925-37 136
87. Hexamethylenetetramine: United States imports for consumption,
1923-37 137
88. Urea: United States imports for consumption, 1919-20 and
1923-37 138
89. Urea: United States imports for consumption, by countries,
1931 and 1933-37 139
90. Thiourea: United States imports through the New York customs
district, 1931-37 140
91. Vinyl acetate, unpolymerized: United States imports for
consumption, 1931-37 141
92. Naphthalene: German imports and exports, by countries, 1929
and 1932-37 144
93. Crude naphthalene: Belgian imports and exports, 1932-37 146
94. Refined naphthalene: Belgian imports and exports, 1932-37 147
95. Crude and refined naphthalene: Netherland imports and exports,
by countries, 1929 and 1932-37 148
96. Refined naphthalene: Canadian imports, by countries, 1928-29
and 1932-37 150
97. Naphthalene: Japanese imports by countries, 1928-29 and 1932-36 150
98. Crude glycerin: United States imports for consumption, by
countries, 1929 and 1931-37 151
99. Refined glycerin: United States imports for consumption,
by countries, 1929 and 1931-37 152
ILLUSTRATIONS
Chart. Derivation of certain synthetic resins 6
Preform press making pellets for use in molding 18
Vacuum cleaner parts of tar-acid resin illustrating the intricate
molded shapes possible 19
Radio cabinet and telephone sets of molded tar-acid resin 19
Cast phenolic resins. Standard shapes and small articles fabricated
from them 20
Laminating sheet press 22
Gears made of laminated tar-acid resin 22
Cocktail lounge using tar-acid laminated decorative materials 23
Thermostat case of molded urea resin 33
Scales case of molded urea resin 33
Airplane cockpit enclosures of cast acrylate resin 36
Spectacle lenses molded to optical prescription from acrylate resin 37
Molded polystyrene resins 42
ACKNOWLEDGMENT
In the preparation of this report, the Commission had the services of
Paul K. Lawrence, Prentice N. Dean, and others of the Commission’s
staff.
1. INTRODUCTION
This survey deals with the several commercially important types of
synthetic resins covered by paragraphs 2, 11, and 28 of the Tariff Act
of 1930 and with the raw materials necessary for their production. It is
made under the general investigatory powers of the Tariff Commission as
provided in section 332 of that act.
The field of synthetic resins is a comparatively new one, most of its
commercial development having occurred within the past 10 years. In 1937
the domestic output was more than 160 million pounds as compared with
slightly more than 10 million pounds in 1927.
The first important patents on synthetic resins were granted about 25
years ago. These patents covered phenolic resins probably intended for
use as substitutes for certain natural resins. It was soon found that
these synthetics offered possibilities of application vastly greater
than the natural materials. At first progress in their application was
slow as is usually the case with new products. During the World War the
shortage of phenol promoted interest in the use of the other tar acids
as raw materials for synthetic resins and intensive research developed
resins from the cresols and higher boiling tar acids. These resins
possessed properties sufficiently different from those made from phenol
to establish them permanently.
In the meantime research on other types of resins was carried on in the
United States and in Europe. The tar-acid resins for molding were the
only commercially important ones on the market until about 1929. About
that time, however, new commercial products began to appear rapidly. Cast
phenolic resins became available as material for novelties of unusual
brilliancy and beauty, the urea resins to meet the requirements for light
colored thermosetting resins in molded articles, and the alkyd resins for
use in new surface coatings which replaced conventional paint materials.
Later there followed a number of thermoplastic materials offering new and
unusual properties. Vinyl resins found application in molded products
and in safety glass. The acrylate resins became the nearest approach to
organic glass yet developed. The polystyrene resins, long in the research
stage, made their commercial appearance in 1937. Resins from petroleum,
from furfural, from adipic acid, and from aniline are on the market. Many
others are under investigation and some of them will undoubtedly become
important.
The versatility of synthetic resins is most unusual. In various uses they
have successfully displaced glass, wood, metal, hard rubber, bone, glue,
cellulose plastics, protein plastics, and conventional paint materials.
They compete with glass in shades and reflectors and offer properties
which will increase their use for this purpose. Cases for scales, radios,
and clocks, formerly of wood and metal, are now made of these synthetic
resins.
Scope and purpose.
This survey deals with the synthetic resins, the nature and trade in the
raw materials necessary for their production, the processes by which they
are made, trade in them in the United States and between nations, and
the nature of the competition which they meet. It does not go into the
details of manufacture of and trade in the multitude of articles made of
synthetic resins but stops at the point where these materials are turned
over to the resin fabricator. The synthetic resins are but one of four
broad groups of organic plastics. The others—natural resins, cellulose
ethers and esters, and protein plastics—are discussed herein only as they
relate to or compete with the synthetic resins.
The purpose of the survey is to bring together in one publication the
available information on synthetic resins so as to provide a basis
for consideration of future tariff problems. Because the industries
involved are comparatively young and are expanding rapidly, their present
day importance is not generally realized. The rapidity with which
the synthetic resin industry is developing causes any comprehensive
report on the subject to be practically out of date before it can be
published. Notwithstanding the progress made each year in the quantity of
production, new applications, and new commercial products, the industry
may be said to be still in the industrial nursery. This circumstance
necessarily limits the period during which any treatment of the subject
will be representative.
Fundamental definitions.
The scope of this report has been stated to include synthetic resins up
to the point where they are further manufactured, and the raw materials
used in producing them. It was also stated that natural resins and
synthetic plastics other than resins, such as the cellulose compounds
and modified rubber compounds, are excluded. The boundaries of these
categories are therefore important.[1]
The term “resin” was formerly applied exclusively to a group of natural
products, principally of vegetable origin, although at least one
important resin, shellac, is of animal origin.[2] These natural resins
are widely used in paints, varnishes, and lacquers for decorative and
protective surface coatings. They also have extensive use in textile
impregnation, adhesives, soap, paper, and in cold-molded articles. In
recent years the natural resins have had to compete with synthetic
products, and each gravitates toward uses which demand the quality or
combination of qualities which it can most completely supply.
A resin may be defined as a semisolid or solid, complex, amorphous
mixture of organic compounds with no definite melting point and no
tendency to crystallize. The resins are characterized by a typical luster
and a conchoidal fracture rather than by definite chemical composition.
The term includes natural resins, such as colophony (ordinary rosin),
copal, damar, lac, mastic, sandarac, shellac, etc., sometimes called gums
or gum resins although none of them are true gums.
A synthetic resin is a resin made by synthesis from nonresinous organic
compounds. The term includes materials ranging from viscous liquids to
hard, infusible, amorphous solids. As a rule synthetic resins possess
properties distinct from those of natural resins. The term “plastics,”
sometimes applied to synthetic resins, also includes many materials which
are not resins.
A plastic is anything possessing plasticity; that is, anything which
can be deformed under mechanical stress without losing its coherence
or its ability to keep its new form. According to this definition the
term includes such materials as putty, cement, clay, glass, and metals,
as well as certain modified natural or semisynthetic products, such
as cellulose acetate, cellulose nitrate, and casein more commonly so
designated. To speak of the plastics industries is almost meaningless
because of their enormous scope, including as they do those producing
cement, ceramics, confectionery and rubber, as well as those producing
the semisynthetic products mentioned.
The resin industry embraces two main types of materials, thermoplastic
and thermosetting. Thermoplastic materials are those which, although
rigid at normal temperatures, may be deformed and molded under heat
and pressure. Among such materials are the cellulose esters, acrylate
resins, vinyl resins, polystyrene resins, etc. The recent development of
injection molding has given thermoplastics a new significance.
Thermosetting substances are thermoplastic at some stage of their
existence, but become hard, rigid, and permanently infusible upon the
application of the proper heat and pressure. They are then irreversible
whereas the thermoplastics are reversible. Outstanding among the
thermosetting resins are tar-acid resins, urea resins, and the alkyd
resins.
Tariff history.
The earliest mention of synthetic resins in the tariff laws of the
United States was the provision in group III of the Emergency Tariff Act
of 1916 for a duty of 30 percent ad valorem and 5 cents per pound on
synthetic phenolic resins. None of the non-coal-tar synthetic resins were
specifically mentioned prior to the Tariff Act of 1930.
The Tariff Act of 1922 (par. 28) provided for synthetic phenolic resin
and all resinlike products, solid, semisolid or liquid, prepared from
phenol, cresol, phthalic anhydride, coumarone, indene, or from any other
article or material provided for in paragraph 27 or 1549. The rate of
duty was 60 percent ad valorem based on American selling price or United
States value and 7 cents per pound, with a provision that the ad valorem
rate should be reduced to 45 percent 2 years after the passage of the act.
The Tariff Commission made two investigations of synthetic resins under
section 316 of the act of 1922. The first was undertaken April 16, 1926,
upon complaints of several domestic manufacturers, of unfair methods of
competition and unfair acts in the importation and sale of synthetic
phenolic resin, Form C, and articles made wholly or in part therefrom, in
infringement of the patent rights of the Bakelite Corporation. Following
the investigation, the Commission recommended on May 25, 1927, that
this material (as described under United States Patents No. 942,809 and
1,424,738) be excluded from entry into the United States. Importers
appealed from the findings of the Commission to the Court of Customs
Appeals, and the judicial proceedings were ended on October 13, 1930, by
denial of a writ of certiorari for the Supreme Court of the United States
to review the judgment of the Court of Customs and Patent Appeals. The
latter court had held, among other things, that there was substantial
evidence in support of each finding of the Commission. On November 26,
1930, the Treasury Department issued an order prohibiting the importation
of synthetic phenolic resin, Form C, with certain exceptions. (T. D.
44411.)
The second investigation by the Tariff Commission was instituted
on December 23, 1927, also under section 316 of the act of 1922.
It concerned unfair methods of competition and unfair acts in the
importation into the United States of laminated products of paper or
other materials and insoluble, infusible condensation products of phenols
and formaldehyde. The Commission recommended to the President that, until
March 4, 1929, inclusive, certain products covered by United States
Letters Patent Nos. 1,018,385, 1,019,406, and 1,037,719 be excluded from
entry into the United States. These products were laminated cloth, paper
or the like, combined with insoluble, infusible condensation products
of phenols and formaldehyde. The order of the President prohibiting the
importation was contained in T. D. 42801 issued June 11, 1928.
Under the Tariff Act of 1930, practically no changes were made in the
provisions of paragraph 28 that concern coal-tar synthetic resins.
Paragraph 2 was extended to include, among other things, the resins
(polymers) of certain organic compounds. The only commercial products
covered by this provision are the vinyl resins. The rate of duty was 30
percent ad valorem on foreign value and 6 cents per pound. Under the
trade agreement with Canada, the duty on vinyl acetate, polymerized or
unpolymerized, and on synthetic resins made in chief value therefrom was
reduced to 15 percent ad valorem and 3 cents per pound (effective Jan. 1,
1936).
The Tariff Act of 1930 contains a provision, in paragraph 11, for
synthetic gums and resins not specially provided for, 4 cents per pound
and 30 percent ad valorem on foreign value.
Broadening use of synthetic resins.
The application of synthetic resins has extended into practically every
branch of industry. This marked expansion is not surprising when the
adaptability of these products is considered. Their uses range from
jewelry and bottle closures to building materials; from adhesives and new
types of surface coatings to light reflectors and shades. They are being
substituted for natural materials, such as wood, metal, and glass at an
increasing rate. They have provided new uses for raw materials formerly
used in antiseptics, disinfectants, explosives, embalming fluids,
fertilizers, moth repellants, and as solvents. The speed of expansion
of their use in resin manufacture has been such as to create a serious
shortage of some of these raw materials.
New applications for synthetic resins appear almost daily. They are used
in furniture, wall panels, builders’ hardware, electrical fixtures, and
in thousands of small appliances. The automobile industry is probably
the largest single user. An interesting application here is in silent
gears and shaft bearings where the use of synthetic resins makes water
lubrication possible. Other automotive uses are in distributor heads,
horn buttons, gear shift knobs, dome light reflectors, control knobs and
the finishing lacquers. Additional uses contemplated for the near future
are in accelerator pedals and instrument panels. A new type of safety
glass in which vinyl resins are used was introduced in 1936.
In decorative uses remarkable progress has been made. Panels of laminated
resins are widely used in store fronts, lobbies of office buildings,
and hotels; doors faced with this material are in use. The liner _Queen
Mary_ is paneled, in part, with laminated resins, as is the annex to the
Library of Congress. Lamp shades of urea resin are used in many Pullman
cars and are available for home and office use.
Other things being equal, the cheaper a synthetic resin, the more widely
it may be applied as a substitute for other materials. As a result many
an apparently useless byproduct, such as oat hulls which yield furfural,
is either already used or being tested as a source of raw material. Other
materials which have already found a place or may do so, are soybean
meal, sugar, and certain petroleum distillates.
Each of the important groups of synthetic resins has been sponsored by
one or more manufacturers of established reputation and large capital
resources. When a product reaches the commercial stage, after heavy
research cost, its future importance is therefore usually assured.
Relation of synthetic resins to their raw materials.
Most of the commercially important synthetic resins are derived directly
or indirectly from coal. The chart (p. 6) shows the derivation of
certain synthetic resins from the principal raw materials used in their
manufacture and the intermediate products back to the original source of
the material.
The polystyrene resins, for example, are made by polymerizing styrene
or vinyl benzene. Although basically from ethylene and benzene, vinyl
benzene may be formed in several ways. Ethylene is found in the gases
from the destructive distillation of coal but is obtained commercially by
cracking natural gas or petroleum. Styrene, found already formed in the
light oil fractions from coal tar, causes gum-forming in motor benzol and
certain industrial gases.
When coke and lime are mixed and heated in an electric furnace to 2,000°
C., calcium carbide is formed. This compound with water yields acetylene,
the starting point for a long list of important products, including
several types of synthetic resins. When acetylene gas is passed through
acetic acid (itself obtained from acetylene) vinyl acetate is obtained.
If hydrochloric acid is used instead of acetic acid, vinyl chloride is
obtained. These compounds, when polymerized, yield the vinyl resins.
The acrylate resins may be obtained from the same basic raw material
by an entirely different procedure. Synthetic rubber is also derived
from acetylene, as are acetic anhydride and acetic acid (used in making
cellulose acetate plastics) and many other chemicals of commercial
importance.
[Illustration: Derivation of certain synthetic resins.]
When naphthalene (from coal tar) is treated with air at elevated
temperatures, phthalic anhydride is formed. Substituting benzene for
naphthalene yields maleic anhydride. Both of these substances when
condensed with glycerin, a byproduct of the soap industry, yield alkyd
resins.
The tar acids from coal tar, either separated or mixed, when condensed
with formaldehyde give the highly important tar-acid resins. Or if
formaldehyde is condensed with urea, obtained from carbon dioxide and
ammonia, the urea resins are formed.
The chart indicates the synthetic resins which are thermoplastic,
that is, which become plastic again upon reheating, and those which
are thermosetting, that is, pass into an infusible stage at a certain
critical temperature and pressure and do not again become plastic upon
subsequent reheating.
Sources of information.
The data used in this report were obtained from a great variety of
sources. The several American and British trade journals were freely
consulted as were the various text books on this subject. Much of the
information on the domestic industry was obtained by personal contact
with producers and by correspondence. Field work included visits to
most of the domestic producers of resins and a representative group
of fabricators. Information of this type which was nonconfidential or
which could be combined so as not to reveal individual operations was
invaluable. Even where it was such that it could not be published it
became part of the general background.
The data pertaining to the industry in foreign countries were, for the
most part, furnished the Tariff Commission by Department of Commerce
representatives stationed abroad, in response to inquiries by the
Commission.
2. SUMMARY
Growth of the industry.
The coal-tar synthetic resin industry in the United States began on a
small scale some years before the World War. The output then was confined
to a few types of tar-acid resins and the applications were quite limited
until 1927, when certain of the basic patents expired. The output of
about 1.5 million pounds in 1921 had increased to more than 13 million
pounds in 1927 and the average unit value of sales had dropped from
81 cents per pound to 47 cents. Production continued to increase and
the unit value to decrease annually until 1932 when general economic
conditions forced a slight curtailment for 1 year. Since then the annual
increase in volume and variety has been rapid. Production of non-coal-tar
synthetic resins was started on a small scale in 1929 when both urea and
vinyl resins entered the picture. Commercial production of the petroleum
resins began in 1936 and of the acrylate resins in 1937. Table 1 shows
the production and sales of coal-tar resins and of non-coal-tar resins,
from 1921 through 1937.
TABLE 1.—_Synthetic resins: United States production and sales, 1921-37_
---------------------+------------+--------------------------------------
| | Sales
Year | Production +------------+------------+------------
| | Quantity | Value | Unit value
---------------------+------------+------------+------------+------------
| _Pounds_ | _Pounds_ | |
Coal-tar resins:[1] | | | |
1921 | 1,643,796 | 1,674,456 | $1,352,166 | $0.81
1922 | 5,944,133 | 6,415,931 | 4,315,196 | .67
1923-26 | ([2]) | | |
1927 | 13,452,230 | 13,084,313 | 6,094,656 | .47
1928 | 20,411,465 | 20,778,856 | 7,211,958 | .35
1929 | 33,036,490 | 30,660,513 | 10,393,397 | .33
1930 | 30,867,752 | 24,014,093 | 7,323,656 | .30
1931 | 34,179,000 | 29,343,000 | 7,862,000 | .27
1932 | 29,039,000 | 23,891,000 | 5,001,000 | .21
1933 | 41,628,485 | 31,657,653 | 7,238,560 | .23
1934 | 56,059,489 | 43,350,876 | 10,126,849 | .23
1935 | 90,913,162 | 65,923,334 | 12,777,195 | .19
1936 |117,301,780 | 86,213,735 | 17,056,099 | .20
1937 |141,098,844 |108,284,175 | 20,165,064 | .19
| | | |
Non-coal-tar resins: | | | |
1932 | 1,898,000 | 1,787,000 | 796,000 | .45
1933 | 3,571,717 | 3,256,411 | 1,745,102 | .54
1934 | ([2]) | 3,500,829 | 1,491,145 | .43
1935 | ([2]) | ([2]) | ([2]) |
1936 | 15,611,041 | 14,766,640 | 3,591,467 | .24
1937 | 21,005,869 | 18,891,277 | 5,680,600 | .30
---------------------+------------+------------+------------+------------
[1] Does not include resins from adipic acid, coumarone and
indene, hydrocarbon, polystyrene, succinic acid and sulfonamides.
With the exception of coumarone and indene resins in recent years
production of the resins not included was small.
[2] Not publishable. Figures would reveal operations of
individual producers.
Source: Compiled from annual reports of the Tariff Commission on
dyes and other synthetic organic chemicals in the United States.
Many factors have contributed to the growth of the synthetic resin
industry. Among these are the intensive research and development work
carried on by many individuals and firms; their widespread application in
many fields competing with wood, metal, and glass; and the development
of processes for raw materials which have greatly reduced their cost and
made their wider use possible.
_Raw materials._—Although the chief raw materials consumed in the
synthetic resin industry are coal-tar derivatives and formaldehyde, many
others are utilized. The rapid expansion of the industry has created new
demands for materials in increasing quantities and has not only increased
the markets for well-known materials but has resulted in the production
on a huge scale of materials entirely new to commerce. Practically all
the raw materials now used can be derived from a few natural substances,
such as air, water, coal, petroleum crudes, salt, sulphur, and limestone.
The air yields nitrogen which may be converted to ammonia, a raw
material for urea, one of the components of the urea resins. Coal, as
is well known, yields a great variety of substances, many of which are
essential to synthetic resin manufacture. Benzene is the starting point
for synthetic phenol; naphthalene is used to make phthalic anhydride
and maleic anhydride; coke is converted to calcium carbide, which in
turn yields acetylene, acetic acid, and many other synthetics; carbon
monoxide which is converted to methanol and formaldehyde; and the natural
tar acids such as phenol, the cresols, and the xylenols. Limestone is a
component of calcium carbide, and salt yields needed alkalies and acids.
Water is broken down, and the hydrogen is converted to ammonia, methanol,
formaldehyde, and ethylene.
Some idea of the expansion in production of these raw materials whose
principal use is in synthetic resins may be had by comparing the output
in 1923 of tar acids, formaldehyde, phthalic anhydride, maleic anhydride,
urea, vinyl acetate, and vinyl chloride, which amounted to 35 million
pounds, with the output of 270 million pounds in 1936. The manufacture of
these materials is largely by coal-tar distilling companies and makers of
chemicals.
_Resins._—The coal-tar resins are the most important in quantity, value,
and variety of application. This class includes four groups: (_a_) tar
acid, (_b_) alkyd, (_c_) coumarone and indene, and (_d_) polystyrene. Of
these, resins from tar acids (phenol, cresols, and xylenols) are produced
in the largest quantity, the output having increased from about 15
million pounds in 1932 to about 80 million pounds in 1937. In the latter
year about 40 percent of the consumption of tar acid resins was in molded
articles, 25 percent in paint and varnishes, 20 percent in laminated
products, and 15 percent in miscellaneous uses.
The alkyd resins have shown a remarkable increase in output. Production
totaled slightly less than 10 million pounds in 1933; in 1937 it amounted
to about 61 million pounds. Practically all of the alkyds have been
consumed in paints and varnishes.
The coumarone and indene resins have increased steadily over a number of
years and are now one of the most important groups.
The polystyrene resins have been in an experimental stage for a long
time, with the volume of production small. In 1937, however, commercial
production of a water-white product was announced, and it is believed
that the output of these resins will increase sharply in the near future.
The non-coal-tar resins were of little importance prior to 1930 and
production amounted to less than 2 million pounds in 1932. Since then,
however, progress has been rapid, both in types and output. Resins from
urea constitute an important part of this class and the output has
increased practically every year since 1929 when production was started.
Most of the output is used in molded articles where light and pastel
shades are required. In 1936, for the first time, appreciable quantities
were consumed in laminating and in surface coatings.
The vinyl resins have been produced in increasing quantities for the past
8 years. Production reached a new high in 1937, and with the acceptance
of this type of resin for safety glass laminations it is expected that
the output will increase materially in the near future. In 1937 the
application in surface coatings, molded articles, and laminations were of
approximately equal importance.
The acrylate resins are among the newest commercial developments in this
industry. Of the several types now manufactured, one appears valuable in
surface coatings and adhesives and another, in the form of its cast or
molded polymer, in airplane windows, machined articles, and lenses.
Petroleum resins were first produced in commercial quantities in 1936,
but the output in that year was appreciable. These low-priced synthetics
are used in surface coatings, laminations, and miscellaneous uses.
The industry abroad.
World production of synthetic resins at this time is estimated at 300
million pounds annually, of which the United States accounts for 45
percent. Germany produces about 27 percent and Great Britain about 20
percent of the total and a number of countries including France, Italy,
Czechoslovakia, Canada, and Japan produce the remainder. Practically all
types are made in Germany and Great Britain although in lesser quantities
than here. The urea resins originated abroad, as did the acrylates and
polystyrenes.
Commercial development of the synthetic resins abroad has been somewhat
behind that in the United States, although in recent years the increase
there has been so rapid as to seriously affect the international raw
material market. Germany, formerly one of our principal sources of crude
naphthalene, for a time restricted exports of that commodity in order
to conserve the available supply for home consumption, presumably in
alkyd resins. Great Britain, formerly the principal exporter of phenol,
has found it necessary to supplement production of natural phenol with
synthetic phenol. It is possible that in the future similar conditions
may arise in world markets for cresylic acid.
International trade.
International trade in the synthetic resins has been small. Germany has
been the principal exporting country. There are a number of reasons
for the negligible movement of these materials in international trade,
the chief of which are active home markets in the principal producing
countries; the existence of patents of a basic nature which limited
trade to the owners and licencees under them; affiliation of producing
companies in different countries with allocation of the world market; and
high tariff barriers in many countries.