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GB2032938A - Curable Polymer Compositions having Plastisol-type Applications - Google Patents

Curable Polymer Compositions having Plastisol-type Applications Download PDF

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Publication number
GB2032938A
GB2032938A GB7936006A GB7936006A GB2032938A GB 2032938 A GB2032938 A GB 2032938A GB 7936006 A GB7936006 A GB 7936006A GB 7936006 A GB7936006 A GB 7936006A GB 2032938 A GB2032938 A GB 2032938A
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United Kingdom
Prior art keywords
compositions
weight
carbon
methacrylate
initiator
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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GB7936006A
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Roehm GmbH Darmstadt
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Roehm GmbH Darmstadt
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Filing date
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Publication of GB2032938A publication Critical patent/GB2032938A/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/04—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyesters
    • C08F299/0478—Copolymers from unsaturated polyesters and low molecular monomers characterised by the monomers used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/026—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight
    • C08F299/028—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from the reaction products of polyepoxides and unsaturated monocarboxylic acids, their anhydrides, halogenides or esters with low molecular weight photopolymerisable compositions
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
    • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
    • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
    • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The compositions are essentially free of volatile constituents and comprise: A) 10 to 40% by weight of at least one acrylate or methacrylate of formula <IMAGE> in which R represents a hydrogen atom or a methyl group, Alk represents an alkylene group with 2 to 4 carbon atoms, n is an integer from 1 to 5 and R' represents a hydrogen atom or an alkyl, aryl, aralkyl or hydroxyalkyl group with 1 to 8 carbon atoms, B) 10 to 40% by weight of an unsaturated polymer resin having a molecular weight of at least 400, each molecule containing, per 1000 molecular weight units, at least one polymerisable carbon-carbon double bond which is activated by an adjacent carbonyl group, subject to the proviso that each molecule contains a minimum of two such carbon-carbon double bonds, C) at least 50% by weight of a finely divided, insoluble filler; and, if desired, D) at least one free radical-forming initiator. These compositions have similar applications to PVC plastisols, e.g. as coating or adhesive agents, but avoid the disadvantages associated with PVC plastisols, such as liberation of HCl at elevated temperatures. The compositions generally contain a free radical initiator when they are to be cured by heating. A process for the coating of substrates using the above compositions is described.

Description

SPECIFICATION Curable Polymer Compositions The invention is concerned with liquid to pasty, curable polymer compositions.
Compositions based on PVC plastisols are used in many areas of the art. These contain as principal components powdery PVC, a filler and a softener. The compositions are employed principally as covering or sealing formulations or adhesive compounds for metals. Upon heating to 1 20 to 1 800C, the PVC powder dissolves in the softener, this step being referred to as the gelling step. Upon cooling, the compositions assume a hardened condition.
Owing to their ease of processing and low costs, PVC plastisols have enjoyed widespread use despite some disadvantages. One of these disadvantages resides in the liberation of hydrogen chloride upon heating the plastisols to high temperature which can occur, for example, in the spot welding of coated sheets. Frequently, the hydrogen chloride may not be able to escape, in which case, corrosion may occur at the welding point.
German Offenlegungsschrift 2,543,542 describes PVC-free, curable compositions of a polymethacrylate resin, a softener and fillers, although they are substantially more expensive than the customary PVC plastisols.
German Patent 1,253,629 describes filler-containing, curable compositions which contain no PVC and no softener but which preferably contain as binding agents mixtures of methyl methacrylate and its polymers. The compositions are cured by polymerisation of the methyl methacrylate. Since this monomer boils at 1 000C, curing must clearly take place below this temperature. However, at curing temperatures of e.g. 30 to 700C it is not possible to achieve curing times which are comparable to the gelling time of PVC plastisols.
It is an object of the present invention to provide heat-curable polymer compositions which can be processed and cured in a similar way to PVC plastisols, but which do not have the above-described disadvantages associated with the latter plastisols.
According to the present invention we provide curable polymer compositions comprising.
A) 10 to 40% by weight of at least one acrylate or methacrylate of formula
in which R represents a hydrogen atom or a methyl group, Alk represents an alkylene group with 2 to 4 carbon atoms, n is an integer from 1 to 5 and R' represents a hydrogen atom or an alkyl, aryl, aralkyl or hydroxyalkyl group with 1 to 8 carbon atoms, B) 10 to 40% by weight of an unsaturated polymer resin having a molecular weight of at least 400, each molecule containing, per 1000 molecular weight units, at least one polymerisable carboncarbon double bond which is activated by an adjacent carbonyl group, subject to the proviso that each molecule contains a minimum of two such carbon-carbon double bonds; C) at least 50% by weight of a finely divided, insoluble filler; and, if desired, D) at least one radical-forming initiator.
An important feature of the new compositions is that they are essentially free of constituents with a boiling point lying below 1 200C. They are curable by polymerisation without loss of volatile constituents and can be hot-or cold-cured depending on the choice of initiator system. Typical processing conditions for hot-curing are heating to 100 to 1 800C for 5 to 30 minutes, whereby the heating time can be the shorter, the higher the temperature. For cold-curing there are used redox systems, at least one component of which may be added immediately before processing. After curing, the compositions are elastic to tough and are comparable with gelled PVC plastisols within wide ranges. The same applies to the adhesive properties on metal.
The new compositions have a liquid or paste-like consistency.
The acrylates and methacrylates used as component A in the compositions according to the invention generally have boiling points above 1 500C. Examples of these esters include ethyl glycol methacrylate, butyl glycol methacrylate; 2-hydroxyethyl or 2-hydroxypropyl methacrylate and ethyl triglycol acrylate or methacrylate.
The esters mentioned in A) are present in the compositions according to the invention in a homogeneous mixture with the unsaturated polymer resin B) which may be selected from a variety of condensation and addition products in which, for example, carboxylic acid ester groups, ether groups, urethane groups and various other bonding groups can be present. The molecular weight of such compounds is preferably at least 500 and advantageously 1,000 to 10,000. For every 1000 molecular weight units the unsaturated polymer resins contain at least one, preferably up to three polymerisable carbon-carbon double bonds per molecule, the said double bonds being adjacent to, and activated by, a carbonyl group, as is the case, for example, in the acyl groups derived from acrylic, methacrylic, maleic or fumaric acid.To ensure that an effective cross-linking of the resin takes place upon curing, the resins must contain at least two double bonds per molecule. These figures are to be regarded as average values if the polymer resin does not have molecular uniformity, as is frequently the case in practice.
Unsaturated polymer resins of this type may be obtained by various conventional processes.
Especially preferred examples of such resins are unsaturated polyester resins which are obtained by reacting unsaturated dicarboxylic acids. for example maleic or fumaric acid, with polyhydric alcohols such as ethylene glycol, diethylene glycol, glycerin, pentaeythritol and the like. The resins frequently contain proportions of units of saturated and aromatic dicarboxylic acids such as adipic acid, sebacic acid phthalic acid or terephthalic acid. These resins are frequently used, in practice, in admixture with styrene, but should be free of styrene in the compositions according to the invention.
A further group of unsaturated polymer resins which may be employed in the compositions according to the invention are so-called "epoxy acrylates" which are obtained by reacting polyepoxy compounds which unsaturated carboxylic acids, preferably by reaction with acrylic acid or methacrylic acid. The basic epoxy compounds are produced, for example, by condensation of polyhydric phenols, the most well-known representative of which compounds is bisphenol A, with epichlorhydrin. An unsaturated polyester resin is obtained by the addition of acrylic or methacrylic acid to the epoxy groups in the end position.
The so-called "urethane acrylates" are prepared in a similar way. Firstly polyhydroxy compounds such as glycerin, pentaerythritol or especially lower linear polyesters with terminal hydroxyl groups are reacted with an excess of di- or triisocyanates such as toluylene diisocyanate or hexamethylene diisocyanate and unsaturated carboxylic acids or their hydroxyalkyi esters are then added to the remaining isocyanate groups.
There are a number of further condensation and addition processes (for example, the Michael addition) by which unsaturated polymer resins can be produced in the above-mentioned molecular weight range. In many cases the unsaturated groups may be introduced by reaction of a reactive intermediate product with acrylic, methacrylic or maleic acid or their hydroxyalkylates. Maleic acid anhydride can also serve to incorporate unsaturated groups.
A common feature of the unsaturated polymer resins for use in the composition according to the invention is their homogeneous miscibility with the hydroxy esters or ether esters of component A according to the invention as hereinbefore defined. These two constituents can be employed in mixture ratios between 4:1 and 1:4. The consituents form medium to high-viscosity liquids but may assume a paste-like consistency upon the incorporation of fillers. The molecular weight of the unsaturated polymer resin B) can be the higher, the smaller its proportion in the binder mixture of components A and B.
At least 50% by weight of the compositions according to the invention consist of finely divided fillers insoluble in the binder mixtures of components A and B. Inorganic fillers are preferably used, such as e.g. chalk, quartz powder, kaolin, asbestos powder, mica and other mineral powders. Inorganic or organic pigments can also be used, as required.
The compositions according to the present invention which are intended for hot-curing contain a radical-forming initiator. In order to guarantee a sufficient storage stability at room temperature, an initiator which does not decompose significantly at room temperature should be employed. Initiators having half-lives at 50 to 1 600C of 1 hour to 10 minutes are preferred, for example, debenzoyl peroxide, dilauryl peroxide, cumene hydroperoxide and tert.-butyl perbenzoate. Redox systems for coldcuring consist preferably of a tertiary araliphatic amine such as e.g. N,N-dimethyl-p-toluidine or N,Nbis-2-hydroxyethyl-p-toluidine and a peroxide, especially dibenzoyl peroxide. This redox system may be added immediately before processing.However, if desired, one of the components, especially the tertiary amine, can be added upon preparation of the compound and the second component, the peroxide in the preferred case, can be added shortly before processing. The second component can also be added in mixture with a softener, a part of the resin component or of the fillers. The radicals formed from the initiator initiate the polymerisation of the hydroxy ester or ether ester component A.
The carbon-carbon double bonds of the unsaturated polymer resin are included in this polymerisation, so that a uniform binder resin is obtained.
In order to modify the properties of the compositions, various other comonomers can be used, provided that their boiling point is so high that they do not evaporate under the curing conditions and lead to an unpleasant smell. Reference can be made to monomers with acid or basic groups which in many cases bring about an improvement of adhesion to metallic substrates. Bi-functional high-boiling comonomers such as e.g. ethyiene glycol dimethacrylate can also be used as cross-linking agents, in order to reduce sensitivity towards organic solvents.
Softeners, for example phthalic acid or sebacic acid ester, preferably in quantites of 10 to 30% by weight, may be incorporated in the compositions according to the invention in order to improve the elastic properties. As in the preparation of PVC plastisols, the components may be combined in conventional mixing devices and processed into a liquid to pasty, spreadable compound.
The processing of the compositions according to the invention is analogous to that of known PVC plastisols. The compositions may be applied to substrates to be coated by dipping, spraying, pouring, knife-coating or spreading. In the case of coatings they can be applied in layer thicknesses of e.g. 0.05 to 5 mm. The most customary layer thickness is 0.1 to 0.5 mm. The compositions according to the invention are used predominantly on metallic substrates, especially on primed steel sheets. They can also be employed for the glueing of substrates or as sealing compositions for seam jointing, for example in spot welding. Favourable curing conditions generally involve heating to 100 to 2000 C, e.g.
for between 30 minutes at 1000C and 5 minutes at 1 800C.
The following Examples illustrate the present invention.
Example 1 1 mol of an epoxide resin of the composition
is reacted with 2 mol of acrylic acid. The addition product with a molecular weight of 492 is dissolved at 5% to 10% in 2-phenoxyethylacrylate. This binding agent is used to prepare a curable paste: 20 parts by weight of the binding agent 10 parts by weight of dioctyl phthalate 30-40 parts by weight of chalk 0.5 parts by weight of cumene hydroperoxide.
The paste is applied in a thickness of 0.5 to 1 mm to polished iron sheeting and is stoved for 10 minutes at 1 9O0C. A tough elastic coating with good adhesion is obtained.
Examples 2 to 4 Coating compositions are prepared according to the formulation specified in Example 1, but the binding agent contains, instead of 2-phenoxyethylacrylate, in the same quantity: Example 2: hydroxypropyl methacrylate Example 3: 2-benzyloxyethyl acrylate Example 4: triethyleneglycolethylether methacrylate [CH2=C(CH3)-C0-(OC2H4)-0C2H5] The stoved coatings have about the same properties as that prepared according to Example 1.
Example 5 A urethane acrylate (molecular weight 470) of formula
prepared by the addition of 2 mol of 2-hydroxyethyl methacrylate to 1 mol of trimethyl hexamethylene diisocyanate is dissolved at 20% to 30% in 2-phenoxyethylacrylate.
A coating composition is prepared from 20 parts by weight of the above solution 10 parts by weight of dioctyl phthalate 30-40 parts by weight of filler (chalk) 0.5 parts by weight of cumene hydroperoxide.
The composition is applied in a thickness of 0.5 to 1 mm to primed steel sheeting and stoved for 10 minutes at 1 800C. A tough coating with firm adhesion is obtained.
Example 6 A coating composition is composed as follows: 10 parts by weight of a commerical styrene-free unsaturated polyester resin (synthetic resin LTH, Chem. Werke Huls AG), molecular weight 2500, iodine number 26.7, corresponding to 2.6 double bonds per mole, 10 parts by weight of 2-phenoxyethylacrylate, 10 parts by weight of dioctyl phthalate, 3 parts by weight of soft urea resin, 40 parts by weight of chalk, 1 part by weight of 2-hydroxypropyl acrylate, 0.5 parts by weight of 1 ,4-butandiol dimethacrylate, 0.6 parts by weight of cumene hydroperoxide or 1.0 parts by weight of 50% benzoyl peroxide paste.
The composition is applied in a thickness of 0.5 to 1 mm to primed steel sheeting and is stoved for 10 minutes at 1 800C. A toughened coating with firm adhesion is obtained.

Claims (14)

Claims
1. Curable polymer compositions comprising: A) 10 to 40% by weight of at least one acrylate or methacrylate of formula
in which R represents a hydrogen atom or a methyl group, Alk represents an alkylene group with 2 to 4 carbon atoms, n is an integer from 1 to 5 and R' represents a hydrogen atom or an alkyl, aryl, aralkyl or hydroxyalkyl group with 1 to 8 carbon atoms, B) 10 to 40% by weight of an unsaturated polymer resin having a molecular weight of at least 400, each molecule containing, per 1000 molecular weight units, at least one polymerisable carboncarbon double bond which is activated by an adjacent carbonyl group, subject to the proviso that each molecule contains a minimum of two such carbon-carbon double bonds; C) at least 50% by weight of a finely divided, insoluble filler;; and if desired, D) at least one radical-forming initiator.
2. Compositions as claimed in claim 1 wherein the acrylate or methacrylate of component A) is selected from ethyl glycol methacrylate butyl glycol methacrylate, 2-hydroxyethyl and 2-hydroxypropyl methacrylate; and ethyl triglycol acrylate and methacrylate.
3. Compositions as claimed in claim 1 or claim 2 wherein the unsaturated polymer resin of component B) is selected from the reaction products of: A) polyhydric saturated aliphatic alcohols or ether alcohols with unsaturated aliphatic dicarboxylic acids; B) polyepoxy compounds with unsaturated monocarboxylic or dicarboxylic acids or their hydroxyalkyl esters; and C) polyisocyanates with unsaturated monocarboxylic or dicarboxylic acids or their hydroxyalkyl esters.
4. Compositions as claimed in any of the preceding claims wherein the molecular weight of the said unsaturated polymer resin of component B) is 1,000 to 10,000.
5. Compositions as claimed in any of the preceding claims wherein the said unsaturated polymer resin of component B) contains, in each molecule, up to 3 of the said polymerisable carbon-carbon double bonds per 1000 molecular weight units.
6. Compositions as claimed in any of the preceding claims containing an initiator which is capable of forming radicals upon heating.
7. Compositions as claimed in claim 6 wherein the said initiator comprises dibenzoyl peroxide.
8. Compositions as claimed in any of the preceding claims containing a softener in an amount of up to 30% by weight.
9. Compositions as claimed in any of the preceding claims having a liquid or paste-like consistency.
10. Compositions as claimed in any of the preceding claims substantially as herein described in any of the Examples.
11. A process for the coating of a substrate which comprises applying a composition as claimed in any of the preceding claims, including the said initiator D), in the form of a coating and subsequently curing the said coating.
12. A process as claimed in claim 11 wherein the said initiator is capable of forming radicals upon heating, and curing of the said coating is effected by heating to 1000 to 2000 C.
13. A process as claimed in claim 11 or claim 12 wherein the said substrate is a metal substrate.
14. A process as claimed in claim 13 wherein the said substrate is a primed metal substrate.
GB7936006A 1978-10-26 1979-10-17 Curable Polymer Compositions having Plastisol-type Applications Withdrawn GB2032938A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19782846573 DE2846573A1 (en) 1978-10-26 1978-10-26 LIQUID TO PASTE-SHAPED, LOCKABLE PLASTIC MATERIAL

Publications (1)

Publication Number Publication Date
GB2032938A true GB2032938A (en) 1980-05-14

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GB7936006A Withdrawn GB2032938A (en) 1978-10-26 1979-10-17 Curable Polymer Compositions having Plastisol-type Applications

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JP (1) JPS5560512A (en)
DE (1) DE2846573A1 (en)
GB (1) GB2032938A (en)
IT (1) IT1119187B (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0124700A1 (en) * 1983-05-04 1984-11-14 Hüls Aktiengesellschaft Transparent impact-resistant polyvinyl chloride-based moulding masses
EP0220648A3 (en) * 1985-10-29 1989-02-08 DeSOTO, INC. Ultraviolet curable outer coatings for optical fiber
FR2634778A1 (en) * 1988-07-09 1990-02-02 Canon Kk ADHESIVE COMPOSITION
EP0442953A4 (en) * 1988-11-09 1991-10-30 Elvin Merrill Bright Optical plastics and methods for making the same
US5741542A (en) * 1994-04-28 1998-04-21 Minnesota Mining & Manufacturing Company Process of making thermal free-radical cure adhesives
US5976690A (en) * 1995-05-18 1999-11-02 3M Innovative Properties Company Opaque adhesives and method therefor

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
MX173523B (en) * 1981-11-02 1994-03-11 Gencorp Inc IMPROVEMENTS IN THERMOSURING COATING COMPOSITION AND METHOD
EP0114117B1 (en) * 1983-01-18 1986-09-24 Loctite Corporation Rapid cure acrylic monomer systems
JPS59174620A (en) * 1983-03-23 1984-10-03 Nippon Oil & Fats Co Ltd Thermosetting resin for dispersing pigment
US5596036A (en) * 1991-06-14 1997-01-21 Sandoz Ltd. Hardenable acrylic monomer compositions
DE4121686A1 (en) * 1991-06-29 1993-01-07 Nokia Deutschland Gmbh METHOD FOR gluing the voice coil carrier to the diaphragm of a speaker
DE4237957A1 (en) * 1991-11-15 1993-05-19 Herberts Gmbh Stone impact-resistant coating materials - contain specified unsatd. polyester, polyunsaturated reactive diluent, heat-activated radical initiator and opt. fillers, pigments, solvent etc.
US5712337A (en) * 1992-06-11 1998-01-27 Mbt Holding Ag Hardenable acrylic monomer compositions

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0124700A1 (en) * 1983-05-04 1984-11-14 Hüls Aktiengesellschaft Transparent impact-resistant polyvinyl chloride-based moulding masses
US4581414A (en) * 1983-05-04 1986-04-08 Huels Aktiengesellschaft Transparent, impact-resistant molding compositions based on polyvinyl chloride
EP0220648A3 (en) * 1985-10-29 1989-02-08 DeSOTO, INC. Ultraviolet curable outer coatings for optical fiber
FR2634778A1 (en) * 1988-07-09 1990-02-02 Canon Kk ADHESIVE COMPOSITION
US5439956A (en) * 1988-07-09 1995-08-08 Canon Kabushiki Kaisha Thermo-curable and ultraviolet-curable adhesive capable of high precision bonding
EP0442953A4 (en) * 1988-11-09 1991-10-30 Elvin Merrill Bright Optical plastics and methods for making the same
US5319007A (en) * 1988-11-09 1994-06-07 Bright Elvin M Optical plastics and methods for making the same
US5741542A (en) * 1994-04-28 1998-04-21 Minnesota Mining & Manufacturing Company Process of making thermal free-radical cure adhesives
US5976690A (en) * 1995-05-18 1999-11-02 3M Innovative Properties Company Opaque adhesives and method therefor

Also Published As

Publication number Publication date
DE2846573A1 (en) 1980-05-08
IT1119187B (en) 1986-03-03
IT7968879A0 (en) 1979-09-27
JPS5560512A (en) 1980-05-07

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