JPH05279437A - Photo-setting resin composition and laminated film - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent adhesivity and flexibility and free from the bleeding of a photo-polymerization initiator because of the absence of low-molecular photo-polymerization initiator by compounding a specific high-molecular photo-polymerization initiator to a resin component such as di(meth)acrylate monomer. CONSTITUTION:The objective composition free from low-molecular photo-polymerization initiator is produced by compounding (A) 5-80 pts.wt. of a halogenated polyester resin and/or a halogenated polyester (meth)acrylate as a photo-polymerization initiator to (B) 20-95 pts.wt. of a di(meth)acrylate monomer and/or di(meth)acrylate other than halogenated polyester (meth)acrylate. The component A is preferably a halogenated polyester containing halogen directly bonding to benzene nucleus or alicyclic structure and the component B is e.g. triethylene glycol diacrylate or dipentaerythritol pentaacrylate.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a photocurable resin composition and a laminated film. More specifically, from a photocurable resin composition which uses a polyester resin having a halogen atom in the molecule and / or a halogenated polyester (meth) acrylate as a photoinitiator and does not use a low molecular weight photoinitiator, and the same composition The present invention relates to a laminated film having a cured layer as an adhesive layer.

When this photocurable resin composition is used, the obtained cured product is a plastic molded product similar to the cured product obtained from the photocurable resin composition containing a low molecular weight photoinitiator which has been conventionally used. It has excellent characteristics in terms of adhesion to objects and flexibility and is the same as conventional ones. Furthermore, since the elution amount of the photoinitiator in the extraction test is small, it is useful especially when used as a film for food packaging.

[Prior Art]

Generally, a plastic material has its flexibility,
It is used in a wide range of fields due to its workability. However, since the surface lacks hardness and scratch resistance, a hard coat layer is usually provided in many cases. In order to provide the hard coat layer on the surface of the plastic material, there is a method of applying a coating layer made of a photocurable resin composition. When the photocurable resin composition is used, one type of urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, or the like, which usually has one or more acrylic groups or methacrylic groups in the molecule, or Used as a main resin component that is a mixture of two or more types.

Pigments, dyes, etc. are mixed arbitrarily with this main resin component to the extent that they do not inhibit photocuring, but another essential component is a photopolymerization initiator. Conventionally, a low molecular weight compound having a function of generating radicals has been used as a photopolymerization initiator.

The following are more specific compounds. 2,2-dimethoxy-2-phenylacetophenone, acetophenone, benzophenone, xanthone, fluorenone, benzaldehyde, anthraquinone, triphenylamine, 3-methylacetophenone, 4-chlorobenzophenone, 4,4'-dimethoxybenzophenone,
N, N, N ', N'-tetramethyl-4,4'-diaminobenzophenone, benzoinpropyl ether, benzyl dimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one , 2-hydroxy-2-methyl-1-phenylpropan-1-one, and other thioxanthone compounds were used.

[Problems to be Solved by the Invention]

However, all of the above photopolymerization initiators that are currently mixed with a photocurable resin and used are low molecular weight compounds. When the photocurable resin composition containing a compound as described above is applied to a packaging film for foods as a binder for paints or inks for printing, or as an adhesive for laminated films, the following is obtained. Cause problems. That is, when the low molecular weight photopolymerization initiator used is transferred to a food product in contact with it, or when the container or laminated film after application of the coating has been stored for a long period of time, the photopolymerization initiator is used as a container or There is a possibility that a phenomenon called "so-called bleeding" that elutes on the surface of the laminate film may occur. Therefore, not only photopolymerization initiators but also generally strict standards are applied to containers and laminated films used for foods. For example, the FDA standard in the United States is well-known, and the extract amount is 50 ppb or less.

[Object of the Invention]

In order to solve the above problems, the present invention contains a halogenated polyester resin and / or a halogenated polyester (meth) acrylate as an essential component, and a conventional low molecular weight photoinitiator is added. A non-photocurable resin composition and a laminated film having a cured layer of the composition as an adhesive layer.

[Means for Solving the Problems]

As a result of intensive studies by the present inventors in order to achieve the above object, the present invention has been completed. That is,
The present invention relates to “(a) one or more kinds of halogenated polyester resin and / or halogenated polyester (meth) acrylate 5 to 80 parts by weight (b) di (meth) acrylate monomer other than halogenated polyester (meth) acrylate and / Or di (meth) acrylate oligomer 20 to 95 parts by weight as an essential component, and a low molecular weight photoinitiator is not added, a photocurable resin composition characterized by the above-mentioned "
And “(a) one or more kinds of halogenated polyester resin and / or halogenated polyester (meth) acrylate 5 to 80 parts by weight (b) di (meth) acrylate monomer other than halogenated polyester (meth) acrylate and / or di (Meth) acrylate oligomer 20 to 95 parts by weight as an essential component, and a low molecular weight photoinitiator is not added, a cured layer formed from a photocurable resin composition as an adhesive layer Having a laminated film ”.

The point of the present invention is that, in a laminate film having a photocurable resin composition and an adhesive layer formed from the photocurable resin composition, the photopolymerization initiator may be transferred to a food product in contact with it, or "so-called bleeding". In order to prevent the phenomenon called "", only a polymer having a halogen atom in the molecule is added as a photopolymerization initiator, and a low molecular weight photopolymerization initiator is not added to the composition. .. The present invention will be described in detail below. In the present invention, the polymer having a halogen atom in the molecule which can be added to the photocurable resin and used as a photopolymerization initiator is a halogenated polyester and / or a halogenated polyester (meth) acrylate. Particularly preferred is a halogenated polyester in which a halogen atom is directly bonded to a benzene nucleus or an alicyclic structure.

Such a halogenated polyester resin is manufactured as follows. That is, a polyvalent carboxylic acid or an anhydride thereof and at least one of polyhydric alcohols used when synthesizing a general polyester resin may be halogenated.
At that time, some of the non-halogenated components may be copolymerized. Halogenated polyvalent carboxylic acids or their anhydrides include 1,4,5,6,7,7-hexachloro-bicyclo [2,2,1] hept-5-ene-2,3-dicarboxylic acid, 1,4,5,6,7,7-hexachloro-bicyclo [2,2,1] hept-5-ene-2-carboxylic acid, 4,4 '-[2,3,5,6
2 ', 3', 5 ', 6'-Octobromo-1,1'-di (3-carboxypropoxy)] biphenyl, 2,4
6-trichlorophenoxy-acetic acid, 4- (pentabromophenoxy) -butyric acid, 2,2-bis- [3,5-dichloro-4- (2-carboxyethoxy) phenyl] propane, 1,4,5,6. 7,7-Hexachloro-bicyclo [2,2,1] hept-5-ene-2-acetic acid, 1,4
5,6,7,7-hexachloro-bicyclo [2,2,2
1] hept-5-ene-2-pelargonic acid, 1,4
5,6,7,7-hexachloro-bicyclo [2,2,2
1] hept-5-ene-2-acrylic acid, 1,4,5,
6,7,7-Hexachloro-bicyclo [2,2,1] hept-5-ene-3-methyl-2-carboxylic acid, 3,5
-Dibromosalicylic acid or its anhydride, tetrachlorophthalic acid or its anhydride, tetrabromophthalic acid or its anhydride, dichloromaleic acid or its anhydride, etc.

The non-halogenated common carboxylic acids used as a mixture or their anhydrides include acetic acid, propionic acid, butyric acid, vinyl acetic acid, acrylic acid, methacrylic acid, benzoic acid and phenoxyacetic acid. Monocarboxylic acid, glutaric acid, succinic acid, adipic acid,
Dicarboxylic acids such as sebacic acid, fumaric acid, maleic acid, citraconic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, tricarboxylic acids such as trimellitic acid, tetracarboxylic acids such as pyromellitic acid Acid etc.

The halogenated polyhydric alcohol is 4,4 '-[2,3,5,6,2', 3 ', 5', 6 '.
-Octachloro-1,1'-di (2- (2-hydroxyethoxy) -ethoxy)] biphenyl or 4,4'-
[2,3,5,6,2 ', 3', 5 ', 6'-octabromo-1,1-di (2- (2-hydroxyethoxy)-
Ethoxy)] biphenyl, 2- (4-chlorophenoxy) -ethane-1-ol, 4- (2,4,6-trichlorophenoxy) -butan-1-ol, 3- (pentachlorophenoxy) -propane-1. -Ol, 3- (pentachlorophenoxy) -propane-1,2-diol, 4,4 '-[2,3,5,6,2', 3 ', 5',
6'-octachloro-1,1-di (2- (2-hydroxyethoxy) -ethoxy)] biphenyl, 4,4'-
[2,3,5,6,2 ', 3', 5 ', 6'-octachloro-1,1-di (2- (2-hydroxyethylamino)] biphenyl, 2,2'-bis [3,3] 5-dichloro-4- (2-hydroxyethoxy) phenyl] propane, 2,2'-bis [3,5-dibromo-4- (2-dihydroxypropoxy) -phenyl] -propane, 1,
4-bis- (2-dihydroxypropoxy) -2,3
5,6-tetrachlorobenzene and the like.

The non-halogenated common alcohols used as a mixture are methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, 2-ethylhexanol, benzyl alcohol, allyl alcohol, trimethylol. Monohydric alcohols such as diallyl ether of propane, ethylene glycol, propylene glycol, 1,
4-butanediol, 1,6-hexanediol, neopentyl glycol, hydrogenated bisphenol A, dihydric alcohols such as tricyclodecane dimethanol, and trihydric alcohols such as glycerol, trimethylolethane and trimethylolpropane. There are alcohols, tetravalent alcohols such as pentaerythritol, and pentavalent or hexavalent alcohols such as dipentaerythritol and sorbitol. The halogenated polyester (meth) acrylate can be obtained by synthesizing the above halogenated polyester and then binding acrylic acid or methacrylic acid to the hydroxyl group at the terminal by esterification.

The essential resin component (b) other than (a) in the photocurable resin composition of the present invention is urethane (meth) acrylate or epoxy (meth) having two or more acrylic groups or methacrylic groups. ) Acrylate or polyester (meth) acrylate, a monomer or oligomer having a (meth) acryloyloxy group, or the like may be used. Examples of the monomer having a (meth) acryloyloxy group include polyether (meth) acrylate-based, polyol (meth) acrylate-based, polyester (meth) acrylate-based, amidourethane (meth) acrylate-based, epoxy (meth) acrylate-based, Urethane (meth) acrylate-based, spiro acetal (meth) acrylate-based and polybutadiene (meth)
Examples thereof include acrylate-based monomers and oligomers.

Specific examples of such compounds include polyether (meth) acrylates synthesized from trimethylolpropane / propylene oxide / acrylic acid and 1,2,6-hexanetriol / propylene oxide / acrylic acid, succinic acid / tricarboxylic acid. Examples thereof include polyester (meth) acrylates synthesized from methylolethane / acrylic acid and adipic acid / 1,6-hexanediol / acrylic acid.

Further, triethylene glycol diacrylate, neopentyl glycol diacrylate,
1,4-butanediol dimethacrylate, hexapropylene glycol diacrylate, trimethylolpropane triacrylate, 2-ethylhexyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl methacrylate, ethylcarbitol acrylate, pentaerythritol tetraacrylate, dipentaerythritol. Tetraacrylate, dipentaerythritol pentaacrylate, 2,2-bis (4-
Acryloyloxydiethoxyphenyl) propane,
(Meth) acrylate or polyol (meth) acrylate such as 2,2-bis (4-acryloyloxypropoxyphenyl) propane, diglycidyl etherified bisphenol A / acrylic acid, diglycidyl etherified polybisphenol A / acrylic acid, triglycidyl Epoxy (meth) such as etherified glycerin / acrylic acid
There are acrylates.

Γ-butyrolactone / N-methylethanolamine / bis (4-isocyanatocyclohexyl) methane / 2-hydroxyethyl acrylate, γ-
Butyrolactone / N-methylethanolamine / 2.6
Amidourethane (meth) acrylates such as tolylene diisocyanate / tetraethylene glycol / 2-hydroxyethyl acrylate, urethane acrylates such as 2,8-tolylene diisocyanate diacrylate, isophorone diisocyanate diacrylate, hexamethylene diisocyanate diacrylate, diary Spiroacetal acrylate synthesized from redene pentaerythritol / 2-hydroxyethyl acrylate, acrylated polybutadiene synthesized from epoxidized butadiene / 2-hydroxyethyl acrylate and the like can also be used.

These can be used alone or
Further, two or more kinds can be mixed and used. Also,
Dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol pentaacrylate, tripentaerythritol hexaacrylate, tripentaerythritol heptaacrylate, or 2,2-bis (4-acryloyloxydiethoxy) Phenyl) propane, 2,2-bis (4-acryloyloxytriethoxyphenyl) propane, 2,
2-Bis (4-acryloyloxydipropoxyphenyl) propane and the like are particularly preferable cross-linking agents because they have very good quick-drying in air when ultraviolet rays are used as active energy rays.

The amount of the halogenated polyester resin used is 5 to 80 parts by weight, preferably 5 to 30 parts by weight, based on the total solid content. If the amount is less than 5 parts by weight, curing by UV or the like is not sufficient, which is not preferable.

On the contrary, even if 80 parts by weight or more is added, the curing characteristics are not so improved. Further, the photocurable resin composition of the present invention may contain an organic solvent which is inert to the resin. Since the viscosity of the composition is reduced by containing the organic solvent, the coating operation can be easily performed.
The organic solvent used is preferably one that does not easily remain in the adhesive layer of the laminate film. Further, additives and polymers which do not affect the physical properties of the composition such as a colorant may be added.

Next, the laminate film of the present invention will be described in detail. The laminated film of the present invention is composed of at least two films, and at least two of them.
It is characterized in that it has a cured layer formed from the photocurable resin composition of the present invention as an adhesive layer between sheets of film and does not contain harmful low molecular weight substances. However, the laminated film of the present invention may contain substances approved by food standards such as pigments, dyes and stabilizers. It is essential that at least one of the at least two films is a film that transmits UV light and the like.

The films may be heat sealable. That is, a vinyl chloride film, a vinylidene chloride film, a polypropylene film, a polyethylene film, a polyamide film, a polyester film, a vinyl acetate film, and a cellophane film whose surface is coated with these materials. The other film to be laminated with the above-mentioned at least one UV transparent film or the like may be any of the various plastic films described above, or an aluminum foil or the like.

The laminated film having a cured layer formed from the photocurable resin composition to which the low molecular weight photoinitiator of the present invention is not added as an adhesive layer is various films which can be subjected to the heat sealing process. It also includes a laminated structure portion formed by independently manufacturing a bag or the like, applying the photocurable resin composition to the end portions, photocuring the composition, and adhering it. The thickness of the coating film when the photocurable resin composition of the present invention to which the low molecular weight photoinitiator of the present invention has not been added is applied to the above various films is several microns to several tens of microns. If the thickness of the coating film is thinner than the above, adhesion may not be sufficient, and conversely, if it is thick, photocuring may not be sufficient. The present invention will be described in more detail by way of examples.

[Example 1] 4 mol of ethylene glycol,
50 parts of polyester resin obtained by dehydration condensation reaction of 3 mol of phthalic anhydride and 3 mol of adipic acid, 30 parts of 1,6 hexanediol diacrylate, chlorinated polyester resin (10 mol of ethylene glycol and 1 mol of phthalic anhydride Acid, 2 moles of adipic acid and 6 moles of tetrachlorophthalic anhydride) 20 parts, ethyl acetate 1
A photocurable resin composition was prepared by mixing 00 parts.

Example 2 7 mol of neopentyl glycol, 2 mol of ethylene glycol, 4 mol of sebacic acid and 4 mol of isophthalic acid were dehydrated and condensed to obtain 3 mol of polyester polyol and TDI-80. 70 parts of urethane acrylate obtained by reacting 2 mol of 2-hydroxyethyl acrylate with 1 mol of urethane prepolymer obtained by reacting 4 mol, chlorinated polyester resin (10 mol of ethylene glycol and 1 mol of anhydrous Phthalic acid, synthesized from 2 mol of adipic acid and 6 mol of tetrachlorophthalic anhydride) 20 parts, 10 parts of 1,6 hexanediol diacrylate and 10 parts of ethyl acetate
A photocurable resin composition was prepared by mixing 0 parts.

Comparative Example 1 10 parts of 1,6 hexanediol diacrylate, 70 parts of the urethane acrylate used in Example 2 and 80 parts of ethyl acetate were mixed to prepare a photocurable resin composition. In addition, the solid content concentrations in the compositions prepared in the above Examples and Comparative Examples are the same.

[Curing test] Each composition described above was treated with cpp / o.
It was applied on the cpp side of pp (clear film) using a # 6 bar coater so that the film thickness would be 3 microns. The clear film coated with the composition was left in an oven at 60 ° C. for 3 minutes to evaporate the ethyl acetate. This was irradiated under a high pressure mercury lamp with an output of 120 W / cm, and the irradiation distance was 10 cm.
(Irradiation from the opp side) and cured at a moving speed of 10 cm / min.

[Adhesive strength test--T-type peeling test by Tensilon] Tensile speed: 200 mm / min Measurement temperature: 20 ° C. Measured on the second day after sample preparation

[Measurement Result: Adhesive Strength] Photocurable resin composition coated film prepared in Example 1: 35 g / 15 mm Photocurable resin composition coated film prepared in Example 2: 15 g / 15 mm The composition coated with the composition prepared in Comparative Example 1 could not be measured because the effect was not progressing at all.

[0030]

EFFECT OF THE INVENTION A laminate film having a photocurable resin composition containing no low molecular weight photoinitiator and a cured layer of the composition as an adhesive layer is obtained.

Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location G03F 7/027 501 511

Claims (5)

[Claims] 1. (a) One or more kinds of halogenated polyester resin and / or halogenated polyester (meth)
Acrylate 5-80 parts by weight (b) Di (meth) acrylate monomer other than halogenated polyester (meth) acrylate and / or di (meth) acrylate oligomer 20-95 parts by weight is contained as an essential component, and low molecular weight light A photocurable resin composition, wherein an initiator is not added. 2. The photocurable resin composition according to claim 1, wherein the halogenated polyester resin is a chlorinated polyester resin. 3. The photocurable resin composition according to claim 1, wherein the halogenated polyester (meth) acrylate is a chlorinated polyester (meth) acrylate. 4. A halogenated polyester resin (a) 5 to 80 parts by weight (b) A di (meth) acrylate monomer and / or a di (meth) acrylate oligomer 20 to 95 parts by weight is contained as an essential component, and a low content A laminate film having, as an adhesive layer, a cured layer formed from a photocurable resin composition to which a molecular weight photoinitiator is not added. 5. The laminate film according to claim 4, wherein the halogenated polyester resin is a chlorinated polyester resin.