CA1337223C - Photopolymerizable compositions of matter - Google Patents
Photopolymerizable compositions of matterInfo
- Publication number
- CA1337223C CA1337223C CA000563852A CA563852A CA1337223C CA 1337223 C CA1337223 C CA 1337223C CA 000563852 A CA000563852 A CA 000563852A CA 563852 A CA563852 A CA 563852A CA 1337223 C CA1337223 C CA 1337223C
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Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09J133/10—Homopolymers or copolymers of methacrylic acid esters
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
- C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
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- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
- C09J175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
- C09J175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
- C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polymerisation Methods In General (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
Compositions of matter containing (a) an oligomeric (meth)acrylate, (b) a monomeric (meth)acrylate, (c) a flexibilizer, (d) a silane adhesion promoter, (e) an .alpha.-aminoacetophenone derivative as photo-initiator and (f) a thioxanthone derivative as photosensitizer for use as adhesives which can be cured in the UV and/or visible range, in particular as adhesives for blister packages and for identity cards or credit cards.
Description
3-16439/+
Photopolymerizable compositions of matter The invention relates to photopolymerizable compositions of matter containing a-aminoacetophenone derivatives as photoinitiators and thioxanthone derivatives as photosensitizers, to the use of these compositions of matter as adhesives which cure within the UV and/or visible range and to a process for bonding surfaces.
Photopolymerizable adhesives of various compositions are known. The use of photopolymerizable adhesives is steadily increasing in impor-tance, since these adhesives, compared with heat-curable adhesives, make possible not only savings in energy but also a more rapid produc-tion of adhesive bonds. One potential field of use for photopolymeri-zable adhesives is in the bonding of materials which are transparent to UV and/or visible radiation, for example various plastic films, to opaque materials, such as cardboard, metals, etc. Adhesive bonds of this type are made, for example, in the production of blister pack-ages, identity cards or credit cards. At the present time, however, the majority of these bonds are still produced with the use of heat-curable adhesives.
Swiss Patent Specification 560,594 describes a process for the pre-paration of composite materials, for example packages, using photo-curable adhesives, for bonding a material transparent to light to a material opaque to light. The adhesives used preferably contain an unsaturated polyester and an acrylate ester and can also contain a polymerization accelerator, for example an organic cobalt salt or a tertiary amine, and a photosensitizer, for example propiophenone or naphthalene derivatives.
13~722~
Swiss Patent Specification 655,476 describes a process for bonding blister packages using an adhesive which can be cured by means of UV
radiation, but does not contain any information on the composition of the adhesive.
Blister packages and also identity cards and credit cards [cf. Kunst-stoffe 77, 880 (1987)] are usually prepared from PVC sheeting, but this material is being increasingly replaced, i.a. for reasons of en-vironmental protection, by other types of polymer, for example poly-styrene, polyacrylonitrile, polyethylene terephthalate, polyamides, polyolefines or polycarbonates. Whereas PVC only absorbs UV radiation in the relatively short-wave range (60~ transmission at approx.
300 nm), the other polymers mentioned are in some cases also opaque to relatively long-wave UV radiation. One consequence of this is that, when using sheeting materials of this type, commercially available UV
adhesives exhibit a considerable retardation in the polymerization rate and also shortcomings in adhesion. These problems can be solved by using certain compositions of matter containing suitable photo-initiators and photosensitizers.
The present invention relates to compositions of matter containing(a) an oligomeric (meth)acrylate, (b) a monomeric (meth)acrylate, (c) a flexibilizer, (d) a silane adhesion promoter, (e) an a-aminoaceto-phenone derivative as photoinitiator and (f) a thioxanthone derivative as photosensitizer, and wherein the composition of matter comprises 10 to 60 parts by weight of the component (a), 10 to 50 parts by weight of the component (b), 5 to 40 parts by weight of the component (c), 0.1 to 10 parts by weight of the component (d), 0.5 to 10 parts by weight of the component (e) and 0.01 to 5 parts by weight of the component (f), the total amount of the components (a) to (f) and any further additives adding up to 100 parts by weight.
The invention also relates to the use of the compositions of matter of the type defined as adhesives which photocure in the UV range and/or in the visible range and to a process for bonding two or more sub-strates at least one of which is a substrate transparent to UV and/or visible light, ~i) the composition of matter according to the inven-tion being applied to at least one of the surfaces to be bonded, (ii) the surfaces to be bonded being brought into contact with one another, ( iii) the arrangement be~ng compressed, if necessary, and (iv) the bond being cured by means of irradiation through the material transparent to radiation. The process according to the invention is particularly suitable for the production of blister packages, identity cards and credit cards.
The preferred amounts of the components (a) to (f) in the compositions of matter according to the invention are as follows:
preferably 15 to 40 parts by weight of the component (a);
preferably 20 to 40 parts by weight of- the componént (b);
preferably 1(3 to 3() parts by weight of the component (c);
preferably 0.5 to 5 parts by weight of the component (d);
preferably 1 to 6 parts by weight of the component (e) and preferably 0.1 to 3 parts by weight of the component ( f), the total amount of the components (a) to (f) and any possible further additives adding up to 100 parts by weight.
The components (a) and (b), according to the invention, i.e. the oligomeric and monomeric (meth)acrylates, respectively, are esters of acrylic or methacrylic acid.
The oligomeric acrylate or methacrylate (a) preferably contains at least one, in particular at least two, groups of the formula I
CHz~--C0~ (I) in which R is hydrogen or methyl, and is a polyether-acrylate, a poly-ester-acrylate, a polyester-urethane-acrylate, an epoxide-acrylate and, in particular, a urethane-acrylate.
Suitable compounds of the type mentioned are known to those skilled in the art and can be prepared in a known manner. They are descri~3ed, for example, in US Patents 3,380,831, 3,297,745, 4,129,488 and 3,586,5~6 to 3,586,530. Products of this type are also available com-mercially. Urethane-acrylates are available, for example, under the name EBECRYL6~) (UCB, Belgium) or Uvithane~ (Morton Thiokol, USA).
They are prepared, for example, by masking prepolymers having isocya-nate end groups with hydroxyalkyl acrylates. In general, the molecu-lar weight of oligomers of this type is within the range from 500 to 5000, in partic~llar 1000 to 2000, but products of lower molecular weights and also of molecular weights up to about 10,000 are also used.
B
~ 4 ~ 133~223 The preferred monomeric acrylates or methacrylates (b) contain at least one group of the formula I and are derived from aliphatic, cycloaliphatic, alicycloaliphatic, araliphatic or heterocyclic-aliphatic monohydric or polyhydric alcohols; from hydroxycarboxylic acids; from hydroxyalkylamines or from hydroxyalkyl nitriles.
Alkyl acrylates or methacrylates, hydroxyalkylacrylates or methacry-lates, or, in particular, cycloalkyl acrylates or methacrylates are particularly preferred as the component (b).
In general, acrylate esters are preferred to methacrylates as compo-nents (a) and (b) according to the invention.
The monomeric (meth)acrylates (b) can contain one or more double bonds. The following are examples of suitable monomeric compounds:
methyl, ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl and n-dodecyl acrylate and methacrylate, 2-hydroxy-ethyl, 2-hydroxypropyl and 3-hydroxypropyl acrylate and methacrylate, 2-methoxyethyl, 2-ethoxyethyl, 2-ethoxypropyl and 3-ethoxypropyl acrylate and methacrylate, allyl acrylate and methacrylate, glycidyl acrylate and methacrylate, cyclopentyl and cyclohexyl acrylate and methacrylate, phenyl acrylate and methacrylate, ethylene glycol di-acrylate, ethylene glycol dimethacrylate, diethylene glycol diacryl-ate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, l,1,1-trimethylolethane triacryl-ate, l,l,l-trimethylolethane trimethacrylate, l,l,l-trimethylolpropane triacrylate, l,l,l-trimethylolpropane trimethacrylate, glycerol tri-acrylate, glycerol trimethacrylate, pentaerythritol diacrylate, pen-taerythritol dimethacrylate, pentaerythritol triacrylate, pentaery-thritol trimethacrylate, pentaerythritol tetraacrylate, pentaery-thritol tetramethacrylate, butane-1,3-diol diacrylate, butane-1,3-diol dimethacrylate, butane-1,4-diol diacrylate, butane-1,4-diol dimeth-acrylate, hexane-1,6-diol diacrylate, hexane-1,6-diol dimethacrylate, propane-1,3-diol diacrylate, propane-1,3-diol dimethacrylate, octane-1,8-dioldiacrylate, octane-1,8-diol dimethacrylate, dodecane-1,12-diol diacrylate, dodecane-1,12-diol dimethacrylate, tetrahydrofurfuryl ~ _ 5 _ 1 3 3 7223 acrylate and methacrylate, isobornyl acrylate and meth-acrylate and dicyclopentenyloxyethyl acrylate and methacrylate.
The monounsaturated (meth)acrylates act as reactive diluents. If de-sired, however, the compositions of matter according to the invention can also contain further reactive diluents without (meth)acrylate groups, in particular l-vinyl-2-pyrrolidone.
The amount of reactive diluent which can be used in addition is suit-ably within the range from 0 to 30, in particular 10 to 20, parts by weight, relative to the amounts defined initially of the components (a) to (f).
The polymerizable monomers or mixtures of these monomers must not be gaseous at room temperature; they should therefore be liquid, solid, semi-solid or pasty.
The compositions of matter according to the invention contain a flexi-bilizer as the component (c). This can be a thermoplast, a thermo-plastic rubber or an elastomer. The addition of components of this type in order to increase the adhesive power of the mixture is known per se. As a rule, polymers of this type must carry polar or func-tional groups. These groups can be present as end groups and/or can be incorporated in the skeleton of the molecule.
The thermoplast, thermoplastic rubber or elastomer is preferably se-lected from the group consisting of polyacetal, polyacrylate, poly-methacrylate, polystyrene, polyamide, polyurethane, polyvinyl chlor-ide, polyester (saturated or unsaturated), polyvinyl acetate, poly-vinyl alcohol, polyvinylpyrrolidone, cellulose ester, polybutadiene, polyisoprene or copolymers formed from styrene and acrylate or from styrene and methacrylate, from styrene and butadiene or from styrene and isoprene or terpolymers formed from styrene, butadiene and acrylo-nitrile.
Preferred flexibilizers are elastomers or thermoplastic rubbers, in particular polybutadienes, polyisoprenes, copolymers formed from styrene and acrylates or from styrene and methacrylates,from styrene and butadiene, from styrene and isoprene or from butadiene and acrylonitrile or terpolymers formed from styrene, butadiene and acrylonitrile.
Nitrile rubbers are particularly preferred, for example polymers of the KRNYAC~)type made by Polysar, polybutadiene/acrylonitrile polymers terminated by functional and/or polar groups, for example polymers of the HYCAR~9 type made by Goodrich, particularly the vinyl-terminated types of these, or modified 1,2-polybutadienes, for example polymers of the NISS ~ PB type made by Nippon Soda, particularly the urethane-modified, maleic acid-modified, hydroxyl-modified or carboxyl-modified types.
It is very particularly preferable for the flexibilizer (c) to contain vinyl-terminated groups and to be, in particular, a vinyl-terminated butadiene/acrylonitrile polymer.
A large number of silane adhesion promoters are known to those skilled in the art. The use of compounds of this type in adhesives is des-cribed, for example, by G. Habenicht, "Kleben" ("Adhesive Bonding"), pages 70-73, Springer Verlag, Berlin 1986.
Preferred adhesion promoters (d) are compounds of the formula II
R10/ (II) in which the R1S independently of one another are a C1-C4alkyl group or a C3-cloalkoxyalkyl group, R2 is a direct bond or a C2-C6alkylene group and X is a reactive radical selected from the groups comprising CH2=CH-, CH2=CHfl -, CH2=C - ~-, HS-, H2~-, H2NCH2CH2NH-, HO-, C~2~CHCH20- and \ /
Compounds of this type are available on the market, for example from Union Carbide USA. Particularly preferred adhesion promoters are com-pounds containing a glycidyloxy group, in particular Y-glycidyloxypro-pyltrimethoxysilane. It is also possible to use silanes of the type described in German Offenlegungsschrift 2,934,550, containing imide groups.
cl-Aminoacetophenone derivatives are used as the photoinitiator (e) in the compositions of matter according to the invention. These com-pounds are known from EP-A-3,002 as photoinitiators for ethylenically unsaturated compounds. Compounds which contain, in the 4-position of the phenyl radical, a substituent containing sulfur, oxygen or nitro-gen are described in EP-A 88,050, EP-A 117,233 and EP-A 138,754 as photoinitiators for pigmented, photocurable systems, for example for UV-curable printing inks.
Preferred photoinitiators (e) are compounds of the formula III
Ar--1~--~--N~ (I II) in which Ar is a C6-C14aryl group which is unsubstituted or substituted by one or more of the radicals halogen, hydroxyl, Cl-C4alkyl, Cl-C4-alkoxy, Cl-C4alkylthio, Cl-C4alkylamino, Cl-C4dialkylamino or N-Morpho-lino R3 and R4 independently of one another are hydrogen, Cl-C8alkyl, C5-C6cycloalkyl or c7-c9phenylalkyl and R5 and R6 independently of one another are hydrogen or Cl-Cgalkyl~ Cs-C6cycloalkyl or C7-Cgphenyl-alkyl, each of which is unsubstituted or substituted by Cl-C4alkoxy groups, or R5 and R6 together are C3-c7alkylene which can be inter-rupted by ~-, -S- or -N(R7)-, and R7 is hydrogen or Cl-C4alkyl.
Compounds of the formula III which are particularly preferred are those in which Ar is p-N-morpholinophenyl, p-Cl-C4alkoxyphenyl or p-Cl-C4alkylthiophenyl~ in particular p-methoxyphenyl of p-methylthio-phenyl, R3 and R4 independently of one another are C1-C4alkyl or benzyl and R5 and R6 are each methyl or, together wi th the nitrogen atom to which they are attached, are an N-morpholino radical.
The following are examples of suitable photoinitiators:
CS ~ 0 0~
H3CO--~ \o H3CS~ N\ /0 0/ ~ -N(CH2CH20CH3)2 (H3C)zN~ -N(CH3)2 ,_. .=. H3 H3 The compositions of matter according to the invention contain thioxan-thone derivatives as photosensitizers (f). Examples of suitable thio-xanthone derivatives are the substituted thioxanthones described in German Offenlegungsschrift 2,811,755, German Offenlegungsschrift 3,018,891, EP-A 33,720 and EP-A 167,489. Preferred thioxanthones are those which are substituted by one or more halogen atoms or by one or more Cl-C12alkylcarbonyl or Cl-C12alkoxycarbonyl groups.
Thioxanthone photosensitizers are also available, for example, under the name Quantacure~(Ward-Blenkinsop, Middlesex, GB) or Kayacure~
(Nippon Kayaku, Japan).
The following are examples of suitable thioxanthone derivatives: 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-dodecylthioxanthone, l-methoxycarbonylthio-xanthone, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)-thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methyl-thioxanthone, l-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chloro-thioxanthone, l-ethoxycarbonyl-3-ethoxythioxanthone, l-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfurylthioxanthone, 3,4-di-[2-(2-methoxyethoxy)ethoxycarbonyl]-thioxanthone, l-ethoxycar-bonyl-3-(1-methyl-1-morpholinoethyl)-thioxanthone, 2-methyl-6-ethoxy-carbonylthioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6-(1,1-dimethoxybenzyl)-thioxanthone, 2-morpholinomethylthio-xanthone and 2-methyl-6-morpholinomethylthioxanthone.
9 133722~
Mixtures of different components (a) to (f) can also be employed in each case in the compositions of matter according to the invention.
As further customary additives, the mixtures according to the inven-tion can also contain plasticizers, reinforcing agents, for example glass fibres, boron fibres, mineral silicates, powdered quartz, hy-drated aluminium oxide or aluminium powder platelets, and also pig-ments and dyes, for example titanium dioxide, thixotropic agents, flow control agents, such as silicones, waxes and stearates, antioxidants and light stabilizers, particularly of the sterically hindered amines (HALS), type.
The compositions of matter according to the invention are particularly suitable for use as photocurable adhesives. As a result of using the special photoinitiator/photosensitizer combination, curing by means of radiation within the relatively long-wave UV range and/or within the visible range of the spectrum and also in daylight (i.e. without an artificial source of light) is also possible, so that materials which absorb UV radiation, for example various plastics, and inorganic glasses can be bonded within a short time.
The application of the adhesive composition of matter is effected in a manner known per se. The layer thickness of the adhesive film here is, in general, not more than 500 ~m, preferably 40 to 120 ~m. If it is advantageous, however, it is also possible to cure substantially thicker layers by irradiation.
Before being coated with the adhesive composition of matter, the surfaces to be bonded can, if it is advantageous, be degreased and roughened.
When the coated surfaces have been joined together, they are, if app-ropriate, compressed or clamped and are cured by means of irradiation through the material, which is at least partly transparent in the UV
range. In general, curing is effected within about 0.1 to 30 seconds, depending on the light source, the material to be bonded and the adhesive used.
A large number of very different types of light sources are used for irradiating the adhesive bonds. Both point sources and sheet-like radiating systems (lamp carpets) are suitable. The following are examples: carbon arc lamps, xenon arc lamps, mercury vapour lamps, if appropriate doped with metal halides (metal halogen lamps), fluore-scent lamps, argon incandescent lamps, electronic flash lamps and photographic flood-light lamps. As mentioned, curing can also be carried out in daylight.
The distance between the source of radiation and the composition of matter according to the invention can vary, depending on the end use and the source and strength of the radiation, for example from ~1 cm to 150 cm, preferably from 3 cm to 30 cm. It will readily be under-stood that, when curing in daylight, the source of radiation is, of course, at a greater distance.
Surfaces suitable for bonding are the surfaces of metals, such as steel, aluminium and its alloys, for example with magnesium or sili-con, copper and its alloys, so-called zincro metal (a zincchromium alloy), polar polymeric materials, such as polyamides, polyurethanes, polyesters, glass fibre-reinforced plastics, wood, glass, ceramics and paper and surfaces which have been finished with coatings. The adhesive can also be used for bonding two materials of different types, for example cardboard or metals to coating films. The only requirement is that at least one of the materials shall be at least partly transparent to UV or visible radiation. The following are some examples of the use of the compositions of matter according to the invention: the production of blister packages, the bonding of plastics films to identity cards, credit cards or cheque cards, the bonding of incandescent bulbs (light bulbs), the bonding of optical components, such as lenses or light guides (optical bonding), and the like.
Preparation of the compositions of matter The compositions used in the illustrative embodiments are prepared as follows: the components are in each case mixed together in a dissolver and are homogenized for not more than 15 minutes at 50 to Example 1 24 parts by weight of an aliphatic urethane-acrylate (EBECRYL5~ 270 made by UCB, Belgium), 35 parts by weight of isobornyl acrylate, 20 parts by weight of 1-vinyl-2-pyrrolidone, 20 parts by weight of a vinyl-terminated butadiene/acrylonitrile polymer (Hyca VTBNX 1300X23 made by BF Goodrich, USA), 1 part by weight of Y-glycidyloxypropyltrimethoxysilane (Union Carbide Corp., USA), 3 parts by weight of a photoinitiator of the formula H3CS~ /0 and 0.25 part by weight of 2,4-diethylthioxanthone.
The adhesion of various types of plastics sheeting to white cardboard is determined by applying an adhesive film of the composition 50 to 100 ~m thick to the sheeting by means of a doctor-knife, and placing the cardboard on this. After the test specimen has been turned round, it is weighted down with a sheet of window glass 8 mm thick.
Curing is effected by irradiating the samples through the sheet of glass by means of an 80 W/cm high-pressure mercury vapour lamp in a Minicure-test apparatus at a distance of 5 to 7 cm. In the course of this, the minimum exposure time required to reach satisfactory adhesion is determined by varying the transport speed. The adhesion is assessed as satisfactory if it is no longer possible to detach the sheeting from the cardboard without causing partial damage to the cardboard.
Irradiation time Sheet material (seconds) PVC (0.35 mm) Polystyrene (0.4 mm) 2.10 very good very good 1.05 very good good 0.50 very good satisfactory 0.20 very good satisfactory Example 2 Example 1 is repeated, except that the composition contains 2-isopropylthioxanthone instead of Z,4-diethylthioxanthone.
The adhesion of various types of sheeting to cardboard printed in blue is determined as described in Example 1.
Sheet material Transport speed Irradiation time (m/minute) (seconds) PVC (0.35 mm) 60 0.35 PVC (UV-stabilized, 0.20 mm) 20 1.05 Polystyrene (0.30 mm) 30 0.75 Polyacrylonitrile (0.30 mm) 30 0.75 Polyethylene terephthalate 40 0.52 (0.40 mm) Example 3 Example 2 is repeated. The adhesion of various types of sheeting to cardboard printed in brown is determined as described in Example 1.
Sheet material Irradiation time (seconds) PVC (0.35 mm) 0.50 PVC (UV stabilized, 0.20 mm) 1.00 Polystyrene (0.30 mm) 1.00 Polyacrylonitrile (0.30 mm) 0.75 Example 4 40 parts by weight of the urethane-acrylate used in Example 1, 27 parts by weight of isobornyl acrylate, 12 parts by weight of 1-vinyl-2-pyrrolidone, 20 parts by weight of the butadiene/acrylonitrile polymer used in Example 1, 1 part by weight of ~-glycidyloxypropyltri-methoxysilane, 3 parts by weight of photoinitiator used in Example 1 and 0.25 part by weight of 2-isopropylthioxanthone.
The tensile shear strength of glass/plastics bonds is determined by applying the adhesive manually to two adjacent plastics sheets approx.
3-4 mm thick and bonding these to a sheet of window glass 8 mm thick (overlapping area 2 x 12.5 x 25 mm). Curing is effected by irradiating the sample through the glass sheet in a Minicure apparatus by means of an 80 W/cm high-pressure mercury vapour lamp at a distance of 6 to 7 cm. The transport speed is 5 m/minute, corresponding to an expo-sure time of 4.2 seconds. After being irradiated, the test speci-mens are stored in the dark at room temperature for 15 minutes. The tensile shear strength to breaking point of the test specimen is then measured by means of a tensile testing machine (Tensometer).
Sheet material Tensile shear strength* (N/mm2) as specified in DIN 53,283 PVC (rigid, grey) 5.5 - 6.5 Polyamide (opaque) 2.0 - 3.0 Polypropylene (rigid, grey) 1.6 - 2.0 Polycarbonate (transparent) 3.5 - 4.0 Aluminium (Anticorrodal lOOB, 1.5 mm) 5.2 - 5.9 * Values from three measurements Example 5 This example illustrates the curing of an adhesive accord-ing to the invention in daylight. The composition of matter described in Example 4 is used, except that 2-methyl-6-ethoxycarbonylthioxan-thone is employed instead of 2-isopropylthioxanthone. The tensile shear strength of glass/aluminium bonds is determined by preparing test specimens analogously to Example 4. Curing is effected through the glass sheet, using daylight behind window glass and at the same time measuring the energy of irradiation by means of a UV radiometer.
The irradiation time in this case depends greatly on the intensity of the daylight in the particular case and is between 30 and 5000 seconds. The tensile shear strengths are shown in the table against the irradiated energy.
- 14 - 13~7 22~
Intensity of light (W/cm2) Tensile shear strength* (N/mm2) as specified in DIN 53,283 0.01 2.6 0.02 3.8 0.03 4.8 0.05 5.5 0.075 5.8 0.10 6.1 0.20 6.9 * Average value from three measurements Example 6 40 parts by weight of the urethane-acrylate used in Example 1, 27 parts by weight of isobornyl acrylate, 12 parts by weight of 1-vinyl-2-pyrrolidone, 20 parts by weight of the butadiene/acrylonitrile polymer used in Example 1, 1 part by weight of ~glycidyloxypropyl-trimethoxysilane, 3 parts by weight of a photoinitiator of the formula 0/ ~ N(CH3)2 \.=./
and 0.30 part by weight of 2,4-diethylthioxanthone.
The adhesion of various plastics sheeting/cardboard bonds is deter-mined by applying an adhesive film at a layer thickness of 50-100 ~m to yellow cardboard by means of a spiral doctor-knife. The appro-priate plastics sheet is applied to this adhesive film and is weighted down with a sheet of flat glass 8 mm thick.
Curing is effected by irradiating the test specimens through the sheet of glass by means of TL05 type (Philips) fluorescent tubes at a dis-tance of 4-6 cm. The exposure times required to effect satisfactory adhesion (cf. EXample 1) of the plastics sheet to the cardboard are shown in the table.
Sheet material Irradiation time ( seconds) PVC (0.35 mm) 10 PVC (UV-stabilized, 0.20 mm) 20 Polystyrene (0.30 mm) 25 Polyacrylonitrile (0.40 mm) 15 Example 7 The composition of matter described in Example 1 is used as described in Example 6 for the production of plastics/cardboard bonds ( yellow card-board), and the latter are tested.
Sheet materialIrradiation time (seconds) PVC (0.35 mm) 5.0 PVC (UV-stabilized, 0.20 mm) 15.0 Polystyrene (0.30 mm) 7.5 Polyacrylonitrile (0.40 mm) 7.5 Example 8 24 parts by weight of the urethane-acrylate described in Example 1, 35 parts by weight of isobornyl acrylate, 20 parts by weight of l-vinyl-2-pyrrolidone, 20 parts by weight of the butadiene/acrylo-nitrile polymer described in Example 1, 1 part by weight of Y-glycidyloxypropyltrimethoxysilane, 3 parts by weight of the photo-initiator described in Example 6 and 0.25 part by weight of 2-chloro-thioxanthone.
The adhesive composition of matter is applied as described in Example 1, and the adhesion of various types of plastics sheeting to white cardboard is tested as in Example 1.
Irradiation time Sheet material (seconds) PVC (0.35 mm) Polystyrene (0.4 mm) 2.10 very good very good 1.05 very good good 0.50 very good satisfactory 0.20 very good satisfactory - 133~ 223 Example 9 The composition of matter described in Example 1 is used, except that 2,4-diethylthioxanthone is replaced by 2-chlorothioxan-thone. The adhesion to cardboard printed in blue is determined by preparing and testing test speciments as in Example 1.
Sheet material Transport speedIrradiation time (m/minute) (seconds) PVC (0.35 mm) 60 0.35 PVC (UV-stabilized, 0.20 mm) 20 1.05 Polystyrene (0.30 mm) 30 0.75 Polyacrylonitrile (0.30 mm) 30 0.75 Polyethylene terephthalate 40 0.52 (0.40 mm) Example 10 The composition of matter described in Example 2 is used in accordance with Example 4 to determine the tensile shear strength of various glass/plastics bonds (plastics sheets 3-4 mm thick/8 mm sheet of glass).
Sheet material Tensile shear strength (N/mm2) as specified in DIN 53,283 ABSl (red) 5.0 - 5.8 SMC2 (white) 5.5 - 6.5 Polycarbonate (transparent) 6.5 - 7.5 Polypropylene (rigid, grey) 2.0 - 3.0 Polyamide (opaque) 3.0 - 4.0 PVC (rigid, grey) 5.5 - 6.5 Aluminium (Anticorodal lOOB, 1.5 mm) 5.3 - 6.1 1: Graft polymer of acrylonitrile and styrene on butadiene polymer 2: Glass fiber laminate prepared using a moulding material composed of unsaturated polyester (sheet moulding compound) Example 11 The composition of matter described in Example 2 is used to bond transparent polycarbonate films (0.17 mm thick) which are used, for example, in the production of identity cards. This is effected by applying a homogeneous film of the adhesive, 70-90 ~m thick, by means of a spiral doctor-knife to a film measuring approx.
~- - 17 - 1 3 3 7 22 3 5 x 5 cm and covering the latter, WitllOUt air inclusions, with a second section of film measuring 5 x 5 cm, a strip of approx. 1 cm over the whole width of the film remaining free from adhesive when the latter is applied. The films are weighted down with a sheet of window glass 8 mm thick and are then cured. Curing is effected by exposure for 8 seconds to an 80 W/cm high-pressure mercury vapour lamp in a Minicure test apparatus, at a distance of 5 to 7 cm. Even immediately after curing, it is no longer possible to separate the bonded films by hand.
Example 12 Example 5 is repeated, using as the adhesive the compo-sition of matter described in Example 2. Curing is effected in day-light (sunny weather). The exposure time and the corresponding measurement of light intensity can be seen from the table.
Exposure timeLight intensity Tensile shear strength* (N/mm2) (seconds) (W/cm2) as specified in DIN 53,283 0.01 2.3-2.8 150 0.05 4.2-4.8 300 0.10 5.3-5.8 600 0.20 6.0-7.0 * Values from three measurements
Photopolymerizable compositions of matter The invention relates to photopolymerizable compositions of matter containing a-aminoacetophenone derivatives as photoinitiators and thioxanthone derivatives as photosensitizers, to the use of these compositions of matter as adhesives which cure within the UV and/or visible range and to a process for bonding surfaces.
Photopolymerizable adhesives of various compositions are known. The use of photopolymerizable adhesives is steadily increasing in impor-tance, since these adhesives, compared with heat-curable adhesives, make possible not only savings in energy but also a more rapid produc-tion of adhesive bonds. One potential field of use for photopolymeri-zable adhesives is in the bonding of materials which are transparent to UV and/or visible radiation, for example various plastic films, to opaque materials, such as cardboard, metals, etc. Adhesive bonds of this type are made, for example, in the production of blister pack-ages, identity cards or credit cards. At the present time, however, the majority of these bonds are still produced with the use of heat-curable adhesives.
Swiss Patent Specification 560,594 describes a process for the pre-paration of composite materials, for example packages, using photo-curable adhesives, for bonding a material transparent to light to a material opaque to light. The adhesives used preferably contain an unsaturated polyester and an acrylate ester and can also contain a polymerization accelerator, for example an organic cobalt salt or a tertiary amine, and a photosensitizer, for example propiophenone or naphthalene derivatives.
13~722~
Swiss Patent Specification 655,476 describes a process for bonding blister packages using an adhesive which can be cured by means of UV
radiation, but does not contain any information on the composition of the adhesive.
Blister packages and also identity cards and credit cards [cf. Kunst-stoffe 77, 880 (1987)] are usually prepared from PVC sheeting, but this material is being increasingly replaced, i.a. for reasons of en-vironmental protection, by other types of polymer, for example poly-styrene, polyacrylonitrile, polyethylene terephthalate, polyamides, polyolefines or polycarbonates. Whereas PVC only absorbs UV radiation in the relatively short-wave range (60~ transmission at approx.
300 nm), the other polymers mentioned are in some cases also opaque to relatively long-wave UV radiation. One consequence of this is that, when using sheeting materials of this type, commercially available UV
adhesives exhibit a considerable retardation in the polymerization rate and also shortcomings in adhesion. These problems can be solved by using certain compositions of matter containing suitable photo-initiators and photosensitizers.
The present invention relates to compositions of matter containing(a) an oligomeric (meth)acrylate, (b) a monomeric (meth)acrylate, (c) a flexibilizer, (d) a silane adhesion promoter, (e) an a-aminoaceto-phenone derivative as photoinitiator and (f) a thioxanthone derivative as photosensitizer, and wherein the composition of matter comprises 10 to 60 parts by weight of the component (a), 10 to 50 parts by weight of the component (b), 5 to 40 parts by weight of the component (c), 0.1 to 10 parts by weight of the component (d), 0.5 to 10 parts by weight of the component (e) and 0.01 to 5 parts by weight of the component (f), the total amount of the components (a) to (f) and any further additives adding up to 100 parts by weight.
The invention also relates to the use of the compositions of matter of the type defined as adhesives which photocure in the UV range and/or in the visible range and to a process for bonding two or more sub-strates at least one of which is a substrate transparent to UV and/or visible light, ~i) the composition of matter according to the inven-tion being applied to at least one of the surfaces to be bonded, (ii) the surfaces to be bonded being brought into contact with one another, ( iii) the arrangement be~ng compressed, if necessary, and (iv) the bond being cured by means of irradiation through the material transparent to radiation. The process according to the invention is particularly suitable for the production of blister packages, identity cards and credit cards.
The preferred amounts of the components (a) to (f) in the compositions of matter according to the invention are as follows:
preferably 15 to 40 parts by weight of the component (a);
preferably 20 to 40 parts by weight of- the componént (b);
preferably 1(3 to 3() parts by weight of the component (c);
preferably 0.5 to 5 parts by weight of the component (d);
preferably 1 to 6 parts by weight of the component (e) and preferably 0.1 to 3 parts by weight of the component ( f), the total amount of the components (a) to (f) and any possible further additives adding up to 100 parts by weight.
The components (a) and (b), according to the invention, i.e. the oligomeric and monomeric (meth)acrylates, respectively, are esters of acrylic or methacrylic acid.
The oligomeric acrylate or methacrylate (a) preferably contains at least one, in particular at least two, groups of the formula I
CHz~--C0~ (I) in which R is hydrogen or methyl, and is a polyether-acrylate, a poly-ester-acrylate, a polyester-urethane-acrylate, an epoxide-acrylate and, in particular, a urethane-acrylate.
Suitable compounds of the type mentioned are known to those skilled in the art and can be prepared in a known manner. They are descri~3ed, for example, in US Patents 3,380,831, 3,297,745, 4,129,488 and 3,586,5~6 to 3,586,530. Products of this type are also available com-mercially. Urethane-acrylates are available, for example, under the name EBECRYL6~) (UCB, Belgium) or Uvithane~ (Morton Thiokol, USA).
They are prepared, for example, by masking prepolymers having isocya-nate end groups with hydroxyalkyl acrylates. In general, the molecu-lar weight of oligomers of this type is within the range from 500 to 5000, in partic~llar 1000 to 2000, but products of lower molecular weights and also of molecular weights up to about 10,000 are also used.
B
~ 4 ~ 133~223 The preferred monomeric acrylates or methacrylates (b) contain at least one group of the formula I and are derived from aliphatic, cycloaliphatic, alicycloaliphatic, araliphatic or heterocyclic-aliphatic monohydric or polyhydric alcohols; from hydroxycarboxylic acids; from hydroxyalkylamines or from hydroxyalkyl nitriles.
Alkyl acrylates or methacrylates, hydroxyalkylacrylates or methacry-lates, or, in particular, cycloalkyl acrylates or methacrylates are particularly preferred as the component (b).
In general, acrylate esters are preferred to methacrylates as compo-nents (a) and (b) according to the invention.
The monomeric (meth)acrylates (b) can contain one or more double bonds. The following are examples of suitable monomeric compounds:
methyl, ethyl, n-propyl, n-butyl, isobutyl, n-hexyl, 2-ethylhexyl, n-octyl, n-decyl and n-dodecyl acrylate and methacrylate, 2-hydroxy-ethyl, 2-hydroxypropyl and 3-hydroxypropyl acrylate and methacrylate, 2-methoxyethyl, 2-ethoxyethyl, 2-ethoxypropyl and 3-ethoxypropyl acrylate and methacrylate, allyl acrylate and methacrylate, glycidyl acrylate and methacrylate, cyclopentyl and cyclohexyl acrylate and methacrylate, phenyl acrylate and methacrylate, ethylene glycol di-acrylate, ethylene glycol dimethacrylate, diethylene glycol diacryl-ate, diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, tetraethylene glycol dimethacrylate, l,1,1-trimethylolethane triacryl-ate, l,l,l-trimethylolethane trimethacrylate, l,l,l-trimethylolpropane triacrylate, l,l,l-trimethylolpropane trimethacrylate, glycerol tri-acrylate, glycerol trimethacrylate, pentaerythritol diacrylate, pen-taerythritol dimethacrylate, pentaerythritol triacrylate, pentaery-thritol trimethacrylate, pentaerythritol tetraacrylate, pentaery-thritol tetramethacrylate, butane-1,3-diol diacrylate, butane-1,3-diol dimethacrylate, butane-1,4-diol diacrylate, butane-1,4-diol dimeth-acrylate, hexane-1,6-diol diacrylate, hexane-1,6-diol dimethacrylate, propane-1,3-diol diacrylate, propane-1,3-diol dimethacrylate, octane-1,8-dioldiacrylate, octane-1,8-diol dimethacrylate, dodecane-1,12-diol diacrylate, dodecane-1,12-diol dimethacrylate, tetrahydrofurfuryl ~ _ 5 _ 1 3 3 7223 acrylate and methacrylate, isobornyl acrylate and meth-acrylate and dicyclopentenyloxyethyl acrylate and methacrylate.
The monounsaturated (meth)acrylates act as reactive diluents. If de-sired, however, the compositions of matter according to the invention can also contain further reactive diluents without (meth)acrylate groups, in particular l-vinyl-2-pyrrolidone.
The amount of reactive diluent which can be used in addition is suit-ably within the range from 0 to 30, in particular 10 to 20, parts by weight, relative to the amounts defined initially of the components (a) to (f).
The polymerizable monomers or mixtures of these monomers must not be gaseous at room temperature; they should therefore be liquid, solid, semi-solid or pasty.
The compositions of matter according to the invention contain a flexi-bilizer as the component (c). This can be a thermoplast, a thermo-plastic rubber or an elastomer. The addition of components of this type in order to increase the adhesive power of the mixture is known per se. As a rule, polymers of this type must carry polar or func-tional groups. These groups can be present as end groups and/or can be incorporated in the skeleton of the molecule.
The thermoplast, thermoplastic rubber or elastomer is preferably se-lected from the group consisting of polyacetal, polyacrylate, poly-methacrylate, polystyrene, polyamide, polyurethane, polyvinyl chlor-ide, polyester (saturated or unsaturated), polyvinyl acetate, poly-vinyl alcohol, polyvinylpyrrolidone, cellulose ester, polybutadiene, polyisoprene or copolymers formed from styrene and acrylate or from styrene and methacrylate, from styrene and butadiene or from styrene and isoprene or terpolymers formed from styrene, butadiene and acrylo-nitrile.
Preferred flexibilizers are elastomers or thermoplastic rubbers, in particular polybutadienes, polyisoprenes, copolymers formed from styrene and acrylates or from styrene and methacrylates,from styrene and butadiene, from styrene and isoprene or from butadiene and acrylonitrile or terpolymers formed from styrene, butadiene and acrylonitrile.
Nitrile rubbers are particularly preferred, for example polymers of the KRNYAC~)type made by Polysar, polybutadiene/acrylonitrile polymers terminated by functional and/or polar groups, for example polymers of the HYCAR~9 type made by Goodrich, particularly the vinyl-terminated types of these, or modified 1,2-polybutadienes, for example polymers of the NISS ~ PB type made by Nippon Soda, particularly the urethane-modified, maleic acid-modified, hydroxyl-modified or carboxyl-modified types.
It is very particularly preferable for the flexibilizer (c) to contain vinyl-terminated groups and to be, in particular, a vinyl-terminated butadiene/acrylonitrile polymer.
A large number of silane adhesion promoters are known to those skilled in the art. The use of compounds of this type in adhesives is des-cribed, for example, by G. Habenicht, "Kleben" ("Adhesive Bonding"), pages 70-73, Springer Verlag, Berlin 1986.
Preferred adhesion promoters (d) are compounds of the formula II
R10/ (II) in which the R1S independently of one another are a C1-C4alkyl group or a C3-cloalkoxyalkyl group, R2 is a direct bond or a C2-C6alkylene group and X is a reactive radical selected from the groups comprising CH2=CH-, CH2=CHfl -, CH2=C - ~-, HS-, H2~-, H2NCH2CH2NH-, HO-, C~2~CHCH20- and \ /
Compounds of this type are available on the market, for example from Union Carbide USA. Particularly preferred adhesion promoters are com-pounds containing a glycidyloxy group, in particular Y-glycidyloxypro-pyltrimethoxysilane. It is also possible to use silanes of the type described in German Offenlegungsschrift 2,934,550, containing imide groups.
cl-Aminoacetophenone derivatives are used as the photoinitiator (e) in the compositions of matter according to the invention. These com-pounds are known from EP-A-3,002 as photoinitiators for ethylenically unsaturated compounds. Compounds which contain, in the 4-position of the phenyl radical, a substituent containing sulfur, oxygen or nitro-gen are described in EP-A 88,050, EP-A 117,233 and EP-A 138,754 as photoinitiators for pigmented, photocurable systems, for example for UV-curable printing inks.
Preferred photoinitiators (e) are compounds of the formula III
Ar--1~--~--N~ (I II) in which Ar is a C6-C14aryl group which is unsubstituted or substituted by one or more of the radicals halogen, hydroxyl, Cl-C4alkyl, Cl-C4-alkoxy, Cl-C4alkylthio, Cl-C4alkylamino, Cl-C4dialkylamino or N-Morpho-lino R3 and R4 independently of one another are hydrogen, Cl-C8alkyl, C5-C6cycloalkyl or c7-c9phenylalkyl and R5 and R6 independently of one another are hydrogen or Cl-Cgalkyl~ Cs-C6cycloalkyl or C7-Cgphenyl-alkyl, each of which is unsubstituted or substituted by Cl-C4alkoxy groups, or R5 and R6 together are C3-c7alkylene which can be inter-rupted by ~-, -S- or -N(R7)-, and R7 is hydrogen or Cl-C4alkyl.
Compounds of the formula III which are particularly preferred are those in which Ar is p-N-morpholinophenyl, p-Cl-C4alkoxyphenyl or p-Cl-C4alkylthiophenyl~ in particular p-methoxyphenyl of p-methylthio-phenyl, R3 and R4 independently of one another are C1-C4alkyl or benzyl and R5 and R6 are each methyl or, together wi th the nitrogen atom to which they are attached, are an N-morpholino radical.
The following are examples of suitable photoinitiators:
CS ~ 0 0~
H3CO--~ \o H3CS~ N\ /0 0/ ~ -N(CH2CH20CH3)2 (H3C)zN~ -N(CH3)2 ,_. .=. H3 H3 The compositions of matter according to the invention contain thioxan-thone derivatives as photosensitizers (f). Examples of suitable thio-xanthone derivatives are the substituted thioxanthones described in German Offenlegungsschrift 2,811,755, German Offenlegungsschrift 3,018,891, EP-A 33,720 and EP-A 167,489. Preferred thioxanthones are those which are substituted by one or more halogen atoms or by one or more Cl-C12alkylcarbonyl or Cl-C12alkoxycarbonyl groups.
Thioxanthone photosensitizers are also available, for example, under the name Quantacure~(Ward-Blenkinsop, Middlesex, GB) or Kayacure~
(Nippon Kayaku, Japan).
The following are examples of suitable thioxanthone derivatives: 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2-dodecylthioxanthone, l-methoxycarbonylthio-xanthone, 2-ethoxycarbonylthioxanthone, 3-(2-methoxyethoxycarbonyl)-thioxanthone, 4-butoxycarbonylthioxanthone, 3-butoxycarbonyl-7-methyl-thioxanthone, l-cyano-3-chlorothioxanthone, 1-ethoxycarbonyl-3-chloro-thioxanthone, l-ethoxycarbonyl-3-ethoxythioxanthone, l-ethoxycarbonyl-3-aminothioxanthone, 1-ethoxycarbonyl-3-phenylsulfurylthioxanthone, 3,4-di-[2-(2-methoxyethoxy)ethoxycarbonyl]-thioxanthone, l-ethoxycar-bonyl-3-(1-methyl-1-morpholinoethyl)-thioxanthone, 2-methyl-6-ethoxy-carbonylthioxanthone, 2-methyl-6-dimethoxymethylthioxanthone, 2-methyl-6-(1,1-dimethoxybenzyl)-thioxanthone, 2-morpholinomethylthio-xanthone and 2-methyl-6-morpholinomethylthioxanthone.
9 133722~
Mixtures of different components (a) to (f) can also be employed in each case in the compositions of matter according to the invention.
As further customary additives, the mixtures according to the inven-tion can also contain plasticizers, reinforcing agents, for example glass fibres, boron fibres, mineral silicates, powdered quartz, hy-drated aluminium oxide or aluminium powder platelets, and also pig-ments and dyes, for example titanium dioxide, thixotropic agents, flow control agents, such as silicones, waxes and stearates, antioxidants and light stabilizers, particularly of the sterically hindered amines (HALS), type.
The compositions of matter according to the invention are particularly suitable for use as photocurable adhesives. As a result of using the special photoinitiator/photosensitizer combination, curing by means of radiation within the relatively long-wave UV range and/or within the visible range of the spectrum and also in daylight (i.e. without an artificial source of light) is also possible, so that materials which absorb UV radiation, for example various plastics, and inorganic glasses can be bonded within a short time.
The application of the adhesive composition of matter is effected in a manner known per se. The layer thickness of the adhesive film here is, in general, not more than 500 ~m, preferably 40 to 120 ~m. If it is advantageous, however, it is also possible to cure substantially thicker layers by irradiation.
Before being coated with the adhesive composition of matter, the surfaces to be bonded can, if it is advantageous, be degreased and roughened.
When the coated surfaces have been joined together, they are, if app-ropriate, compressed or clamped and are cured by means of irradiation through the material, which is at least partly transparent in the UV
range. In general, curing is effected within about 0.1 to 30 seconds, depending on the light source, the material to be bonded and the adhesive used.
A large number of very different types of light sources are used for irradiating the adhesive bonds. Both point sources and sheet-like radiating systems (lamp carpets) are suitable. The following are examples: carbon arc lamps, xenon arc lamps, mercury vapour lamps, if appropriate doped with metal halides (metal halogen lamps), fluore-scent lamps, argon incandescent lamps, electronic flash lamps and photographic flood-light lamps. As mentioned, curing can also be carried out in daylight.
The distance between the source of radiation and the composition of matter according to the invention can vary, depending on the end use and the source and strength of the radiation, for example from ~1 cm to 150 cm, preferably from 3 cm to 30 cm. It will readily be under-stood that, when curing in daylight, the source of radiation is, of course, at a greater distance.
Surfaces suitable for bonding are the surfaces of metals, such as steel, aluminium and its alloys, for example with magnesium or sili-con, copper and its alloys, so-called zincro metal (a zincchromium alloy), polar polymeric materials, such as polyamides, polyurethanes, polyesters, glass fibre-reinforced plastics, wood, glass, ceramics and paper and surfaces which have been finished with coatings. The adhesive can also be used for bonding two materials of different types, for example cardboard or metals to coating films. The only requirement is that at least one of the materials shall be at least partly transparent to UV or visible radiation. The following are some examples of the use of the compositions of matter according to the invention: the production of blister packages, the bonding of plastics films to identity cards, credit cards or cheque cards, the bonding of incandescent bulbs (light bulbs), the bonding of optical components, such as lenses or light guides (optical bonding), and the like.
Preparation of the compositions of matter The compositions used in the illustrative embodiments are prepared as follows: the components are in each case mixed together in a dissolver and are homogenized for not more than 15 minutes at 50 to Example 1 24 parts by weight of an aliphatic urethane-acrylate (EBECRYL5~ 270 made by UCB, Belgium), 35 parts by weight of isobornyl acrylate, 20 parts by weight of 1-vinyl-2-pyrrolidone, 20 parts by weight of a vinyl-terminated butadiene/acrylonitrile polymer (Hyca VTBNX 1300X23 made by BF Goodrich, USA), 1 part by weight of Y-glycidyloxypropyltrimethoxysilane (Union Carbide Corp., USA), 3 parts by weight of a photoinitiator of the formula H3CS~ /0 and 0.25 part by weight of 2,4-diethylthioxanthone.
The adhesion of various types of plastics sheeting to white cardboard is determined by applying an adhesive film of the composition 50 to 100 ~m thick to the sheeting by means of a doctor-knife, and placing the cardboard on this. After the test specimen has been turned round, it is weighted down with a sheet of window glass 8 mm thick.
Curing is effected by irradiating the samples through the sheet of glass by means of an 80 W/cm high-pressure mercury vapour lamp in a Minicure-test apparatus at a distance of 5 to 7 cm. In the course of this, the minimum exposure time required to reach satisfactory adhesion is determined by varying the transport speed. The adhesion is assessed as satisfactory if it is no longer possible to detach the sheeting from the cardboard without causing partial damage to the cardboard.
Irradiation time Sheet material (seconds) PVC (0.35 mm) Polystyrene (0.4 mm) 2.10 very good very good 1.05 very good good 0.50 very good satisfactory 0.20 very good satisfactory Example 2 Example 1 is repeated, except that the composition contains 2-isopropylthioxanthone instead of Z,4-diethylthioxanthone.
The adhesion of various types of sheeting to cardboard printed in blue is determined as described in Example 1.
Sheet material Transport speed Irradiation time (m/minute) (seconds) PVC (0.35 mm) 60 0.35 PVC (UV-stabilized, 0.20 mm) 20 1.05 Polystyrene (0.30 mm) 30 0.75 Polyacrylonitrile (0.30 mm) 30 0.75 Polyethylene terephthalate 40 0.52 (0.40 mm) Example 3 Example 2 is repeated. The adhesion of various types of sheeting to cardboard printed in brown is determined as described in Example 1.
Sheet material Irradiation time (seconds) PVC (0.35 mm) 0.50 PVC (UV stabilized, 0.20 mm) 1.00 Polystyrene (0.30 mm) 1.00 Polyacrylonitrile (0.30 mm) 0.75 Example 4 40 parts by weight of the urethane-acrylate used in Example 1, 27 parts by weight of isobornyl acrylate, 12 parts by weight of 1-vinyl-2-pyrrolidone, 20 parts by weight of the butadiene/acrylonitrile polymer used in Example 1, 1 part by weight of ~-glycidyloxypropyltri-methoxysilane, 3 parts by weight of photoinitiator used in Example 1 and 0.25 part by weight of 2-isopropylthioxanthone.
The tensile shear strength of glass/plastics bonds is determined by applying the adhesive manually to two adjacent plastics sheets approx.
3-4 mm thick and bonding these to a sheet of window glass 8 mm thick (overlapping area 2 x 12.5 x 25 mm). Curing is effected by irradiating the sample through the glass sheet in a Minicure apparatus by means of an 80 W/cm high-pressure mercury vapour lamp at a distance of 6 to 7 cm. The transport speed is 5 m/minute, corresponding to an expo-sure time of 4.2 seconds. After being irradiated, the test speci-mens are stored in the dark at room temperature for 15 minutes. The tensile shear strength to breaking point of the test specimen is then measured by means of a tensile testing machine (Tensometer).
Sheet material Tensile shear strength* (N/mm2) as specified in DIN 53,283 PVC (rigid, grey) 5.5 - 6.5 Polyamide (opaque) 2.0 - 3.0 Polypropylene (rigid, grey) 1.6 - 2.0 Polycarbonate (transparent) 3.5 - 4.0 Aluminium (Anticorrodal lOOB, 1.5 mm) 5.2 - 5.9 * Values from three measurements Example 5 This example illustrates the curing of an adhesive accord-ing to the invention in daylight. The composition of matter described in Example 4 is used, except that 2-methyl-6-ethoxycarbonylthioxan-thone is employed instead of 2-isopropylthioxanthone. The tensile shear strength of glass/aluminium bonds is determined by preparing test specimens analogously to Example 4. Curing is effected through the glass sheet, using daylight behind window glass and at the same time measuring the energy of irradiation by means of a UV radiometer.
The irradiation time in this case depends greatly on the intensity of the daylight in the particular case and is between 30 and 5000 seconds. The tensile shear strengths are shown in the table against the irradiated energy.
- 14 - 13~7 22~
Intensity of light (W/cm2) Tensile shear strength* (N/mm2) as specified in DIN 53,283 0.01 2.6 0.02 3.8 0.03 4.8 0.05 5.5 0.075 5.8 0.10 6.1 0.20 6.9 * Average value from three measurements Example 6 40 parts by weight of the urethane-acrylate used in Example 1, 27 parts by weight of isobornyl acrylate, 12 parts by weight of 1-vinyl-2-pyrrolidone, 20 parts by weight of the butadiene/acrylonitrile polymer used in Example 1, 1 part by weight of ~glycidyloxypropyl-trimethoxysilane, 3 parts by weight of a photoinitiator of the formula 0/ ~ N(CH3)2 \.=./
and 0.30 part by weight of 2,4-diethylthioxanthone.
The adhesion of various plastics sheeting/cardboard bonds is deter-mined by applying an adhesive film at a layer thickness of 50-100 ~m to yellow cardboard by means of a spiral doctor-knife. The appro-priate plastics sheet is applied to this adhesive film and is weighted down with a sheet of flat glass 8 mm thick.
Curing is effected by irradiating the test specimens through the sheet of glass by means of TL05 type (Philips) fluorescent tubes at a dis-tance of 4-6 cm. The exposure times required to effect satisfactory adhesion (cf. EXample 1) of the plastics sheet to the cardboard are shown in the table.
Sheet material Irradiation time ( seconds) PVC (0.35 mm) 10 PVC (UV-stabilized, 0.20 mm) 20 Polystyrene (0.30 mm) 25 Polyacrylonitrile (0.40 mm) 15 Example 7 The composition of matter described in Example 1 is used as described in Example 6 for the production of plastics/cardboard bonds ( yellow card-board), and the latter are tested.
Sheet materialIrradiation time (seconds) PVC (0.35 mm) 5.0 PVC (UV-stabilized, 0.20 mm) 15.0 Polystyrene (0.30 mm) 7.5 Polyacrylonitrile (0.40 mm) 7.5 Example 8 24 parts by weight of the urethane-acrylate described in Example 1, 35 parts by weight of isobornyl acrylate, 20 parts by weight of l-vinyl-2-pyrrolidone, 20 parts by weight of the butadiene/acrylo-nitrile polymer described in Example 1, 1 part by weight of Y-glycidyloxypropyltrimethoxysilane, 3 parts by weight of the photo-initiator described in Example 6 and 0.25 part by weight of 2-chloro-thioxanthone.
The adhesive composition of matter is applied as described in Example 1, and the adhesion of various types of plastics sheeting to white cardboard is tested as in Example 1.
Irradiation time Sheet material (seconds) PVC (0.35 mm) Polystyrene (0.4 mm) 2.10 very good very good 1.05 very good good 0.50 very good satisfactory 0.20 very good satisfactory - 133~ 223 Example 9 The composition of matter described in Example 1 is used, except that 2,4-diethylthioxanthone is replaced by 2-chlorothioxan-thone. The adhesion to cardboard printed in blue is determined by preparing and testing test speciments as in Example 1.
Sheet material Transport speedIrradiation time (m/minute) (seconds) PVC (0.35 mm) 60 0.35 PVC (UV-stabilized, 0.20 mm) 20 1.05 Polystyrene (0.30 mm) 30 0.75 Polyacrylonitrile (0.30 mm) 30 0.75 Polyethylene terephthalate 40 0.52 (0.40 mm) Example 10 The composition of matter described in Example 2 is used in accordance with Example 4 to determine the tensile shear strength of various glass/plastics bonds (plastics sheets 3-4 mm thick/8 mm sheet of glass).
Sheet material Tensile shear strength (N/mm2) as specified in DIN 53,283 ABSl (red) 5.0 - 5.8 SMC2 (white) 5.5 - 6.5 Polycarbonate (transparent) 6.5 - 7.5 Polypropylene (rigid, grey) 2.0 - 3.0 Polyamide (opaque) 3.0 - 4.0 PVC (rigid, grey) 5.5 - 6.5 Aluminium (Anticorodal lOOB, 1.5 mm) 5.3 - 6.1 1: Graft polymer of acrylonitrile and styrene on butadiene polymer 2: Glass fiber laminate prepared using a moulding material composed of unsaturated polyester (sheet moulding compound) Example 11 The composition of matter described in Example 2 is used to bond transparent polycarbonate films (0.17 mm thick) which are used, for example, in the production of identity cards. This is effected by applying a homogeneous film of the adhesive, 70-90 ~m thick, by means of a spiral doctor-knife to a film measuring approx.
~- - 17 - 1 3 3 7 22 3 5 x 5 cm and covering the latter, WitllOUt air inclusions, with a second section of film measuring 5 x 5 cm, a strip of approx. 1 cm over the whole width of the film remaining free from adhesive when the latter is applied. The films are weighted down with a sheet of window glass 8 mm thick and are then cured. Curing is effected by exposure for 8 seconds to an 80 W/cm high-pressure mercury vapour lamp in a Minicure test apparatus, at a distance of 5 to 7 cm. Even immediately after curing, it is no longer possible to separate the bonded films by hand.
Example 12 Example 5 is repeated, using as the adhesive the compo-sition of matter described in Example 2. Curing is effected in day-light (sunny weather). The exposure time and the corresponding measurement of light intensity can be seen from the table.
Exposure timeLight intensity Tensile shear strength* (N/mm2) (seconds) (W/cm2) as specified in DIN 53,283 0.01 2.3-2.8 150 0.05 4.2-4.8 300 0.10 5.3-5.8 600 0.20 6.0-7.0 * Values from three measurements
Claims (19)
1. An adhesive composition of matter comprising (a) an oligomeric (meth)-acrylate, (b) a monomeric (meth)acrylate, (c) a flexibilizer, (d) a silane adhesion promoter, (e) an .alpha.-aminoacetophenone derivative as photo-initiator and (f) a thioxanthone derivative as photosensitizer, and wherein the composition of matter comprises 10 to 60 parts by weight of the component (a), 10 to 50 parts by weight of the component (b), 5 to 40 parts by weight of the component (c), 0.1 to 10 parts by weight of the component (d), 0.5 to 10 parts by weight of the component (e) and 0.01 to 5 parts by weight of the component (f), the total amount of the components (a) to (f) and any further additives adding up to 100 parts by weight.
2. A composition of matter according to claim 1, wherein the oligo-meric (meth)acrylate (a) contains at least one group of the formula I
(I) in which R is hydrogen or methyl, and is a polyether-acrylate, a poly-ester-acrylate, a polyester-urethane-acrylate, an epoxide-acrylate or a urethane-acrylate.
(I) in which R is hydrogen or methyl, and is a polyether-acrylate, a poly-ester-acrylate, a polyester-urethane-acrylate, an epoxide-acrylate or a urethane-acrylate.
3. A composition of matter according to claim 1, wherein the monomeric (meth)acrylate (b) contains at least one group of the formula I ac-cording to claim 2, and is derived from aliphatic, cycloaliphatic, alicycloaliphatic, araliphatic or heterocyclic aliphatic monohydric or polyhydric alcohols; from hydroxycarboxylic acids; from hydroxyalkyl-amines or from hydroxyalkyl nitriles.
4. A composition of matter according to claim 3, wherein the monomeric (meth)acrylate (b) is an alkyl, hydroxyalkyl or cycloalkyl acrylate or an alkyl, hydroxyalkyl or cycloalkyl methacrylate.
5. A composition of matter according to either of claims 2 or 3, wherein the substituent R in formula I is hydrogen.
6. A composition of matter according to claim 1, which, in addition, also contains a reactive diluent.
7. A composition of matter according to claim 6, wherein the reactive diluent is 1-vinyl-2-pyrrolidone.
8. A composition of matter according to claim 1, wherein the flexi-bilizer (c) is an elastomer or a thermoplastic rubber.
9. A composition of matter according to claim 8, wherein (c) is a polybutadiene, a polyisoprene, a copolymer formed from styrene and acrylate or from styrene and methacrylate, from styrene and butadiene, from styrene and isoprene or from butadiene and acrylonitrile, or a terpolymer formed from styrene, butadiene and acrylonitrile.
10. A composition of matter according to claim 9, wherein (c) con-tains vinyl-terminated groups.
11. A composition of matter according to claim 10, wherein (c) is a vinyl-terminated butadiene/acrylonitrile polymer.
12. A composition of matter according to claim 1, wherein the silane adhesion promoter (d) is a compound of the formula II
(II) in which the R1s independently of one another are a C1-C4alkyl group or a C3-C10alkoxyalkyl group, R2 is a direct bond or a C2-C6alkylene group and X is a reactive radical selected from the groups comprising CH2=CH-, , , HS-, H2N-, H2NCH2CH2NH-, HO-, and .
(II) in which the R1s independently of one another are a C1-C4alkyl group or a C3-C10alkoxyalkyl group, R2 is a direct bond or a C2-C6alkylene group and X is a reactive radical selected from the groups comprising CH2=CH-, , , HS-, H2N-, H2NCH2CH2NH-, HO-, and .
13. A composition of matter according to claim 12, wherein the silane adhesion promoter contains a glycidyloxy group.
14. A composition of matter according to claim 1, wherein the photo-initiator (e) is a compound of the formula III
(III) in which Ar is a C6-C14aryl group which is unsubstituted or substi-tuted by one or more of the radicals halogen, hydroxyl, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or C1-C4dialkylamino or N-morpholino, R3 and R4 independently of one another are hydrogen, C1-C8alkyl, C5-C6cycloalkyl or C7-C9phenylalkyl and R5 and R6 indepen-dently of one another are hydrogen or C1-C8alkyl, C5-C6cycloalkyl or C7-C9phenylalkyl, each of which is unsubstituted or substituted by C1-C4alkoxy groups, or R5 and R6 together are C3-C7alkylene which can be interrupted by -O-, -S- or -N(R7)-, and R7 is hydrogen or C1-C4alkyl.
(III) in which Ar is a C6-C14aryl group which is unsubstituted or substi-tuted by one or more of the radicals halogen, hydroxyl, C1-C4alkyl, C1-C4alkoxy, C1-C4alkylthio, C1-C4alkylamino or C1-C4dialkylamino or N-morpholino, R3 and R4 independently of one another are hydrogen, C1-C8alkyl, C5-C6cycloalkyl or C7-C9phenylalkyl and R5 and R6 indepen-dently of one another are hydrogen or C1-C8alkyl, C5-C6cycloalkyl or C7-C9phenylalkyl, each of which is unsubstituted or substituted by C1-C4alkoxy groups, or R5 and R6 together are C3-C7alkylene which can be interrupted by -O-, -S- or -N(R7)-, and R7 is hydrogen or C1-C4alkyl.
15. A composition of matter according to claim 14, wherein Ar is p-N-morpholinophenyl, p-C1-C4alkoxyphenyl or p-C1-C4alkylthiophenyl, R3 and R4 independently of one another are C1-C4alkyl or benzyl and R5 and R6 are each methyl or, together with the nitrogen atom to which they are attached, are an N-morpholino radical.
16. A composition of matter according to claim 15, wherein Ar is p-methoxyphenyl or p-methylthiophenyl.
17. A composition of matter according to claim 1, wherein the photo-sensitizer (f) is a thioxanthone which is substituted by one or more halogen atoms or by one or more C1-C12alkylcarbonyl or C1-C12alkoxy-carbonyl groups.
18. A process for bonding two or more substrates at least one of which is a substrate transparent to UV and/or visible light, wherein (i) the composition of matter according to claim 1 is applied to at least one surface to be bonded, (ii) the surfaces to be bonded are brought into contact with one another, (iii) the arrangement is compressed, if necessary, and (iv) the bond is cured by means of irradiation through the material transparent to radiation.
19. A process according to claim 18, wherein the substrates to be bon-ded are components of a blister package or an identity card or credit card.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CH1439/87-3 | 1987-04-14 | ||
| CH143987 | 1987-04-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1337223C true CA1337223C (en) | 1995-10-03 |
Family
ID=4210487
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000563852A Expired - Fee Related CA1337223C (en) | 1987-04-14 | 1988-04-12 | Photopolymerizable compositions of matter |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0287516B1 (en) |
| JP (1) | JP2745000B2 (en) |
| KR (1) | KR960015811B1 (en) |
| CA (1) | CA1337223C (en) |
| DE (1) | DE3879742D1 (en) |
| HK (1) | HK1002709A1 (en) |
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| ES2110987T3 (en) * | 1990-11-05 | 1998-03-01 | Tokyo Ohka Kogyo Co Ltd | PHOTOPOLYMERIZABLE COMPOSITIONS. |
| JP2764480B2 (en) * | 1991-05-17 | 1998-06-11 | 日本化薬株式会社 | Photopolymer composition for color filter |
| DE69222302T2 (en) * | 1992-03-05 | 1998-04-09 | Japan Inst Advanced Dentistry | PHOTOPOLYMERIZABLE ADHESIVE |
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Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| IE51059B1 (en) * | 1980-07-11 | 1986-09-17 | Loctite Corp | Butadiene toughened adhesive composition |
| DE3365773D1 (en) * | 1982-02-26 | 1986-10-09 | Ciba Geigy Ag | Coloured photo-hardenable composition |
| JPS58204008A (en) * | 1982-05-24 | 1983-11-28 | Hitachi Ltd | Photosensitive resin composition |
| US4599274A (en) * | 1983-03-11 | 1986-07-08 | Denki Kagaku Kogyo Kabushiki Kaisha | Photo-curable adhesive composition for glass lamination and laminated glass and process for its production |
| EP0138754B1 (en) * | 1983-08-15 | 1988-05-25 | Ciba-Geigy Ag | Photocurable compositions |
-
1988
- 1988-04-08 EP EP88810230A patent/EP0287516B1/en not_active Expired - Lifetime
- 1988-04-08 DE DE8888810230T patent/DE3879742D1/en not_active Expired - Fee Related
- 1988-04-12 CA CA000563852A patent/CA1337223C/en not_active Expired - Fee Related
- 1988-04-14 JP JP63092634A patent/JP2745000B2/en not_active Expired - Lifetime
- 1988-04-14 KR KR1019880004261A patent/KR960015811B1/en not_active IP Right Cessation
-
1998
- 1998-03-06 HK HK98101875A patent/HK1002709A1/en not_active IP Right Cessation
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2745000B2 (en) | 1998-04-28 |
| DE3879742D1 (en) | 1993-05-06 |
| EP0287516A2 (en) | 1988-10-19 |
| KR880012720A (en) | 1988-11-28 |
| EP0287516A3 (en) | 1990-09-05 |
| KR960015811B1 (en) | 1996-11-21 |
| EP0287516B1 (en) | 1993-03-31 |
| HK1002709A1 (en) | 1998-09-11 |
| JPS63284213A (en) | 1988-11-21 |
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