JP5853859B2 - Active energy ray-curable adhesive composition for plastic film or sheet - Google Patents

Description

The present invention relates to an active energy ray-curable adhesive composition capable of adhering various plastic films or sheets by irradiation with an active energy ray such as an electron beam or ultraviolet rays and further heating. The present invention relates to an adhesive composition in which a decrease in adhesive strength is extremely small even in a high heat and high humidity atmosphere. The composition of the present invention is suitably used for adhesion of a thin-layer adherend including a plastic film or sheet, and further suitable for production of various films or sheets used for liquid crystal display elements, solar battery backsheets and the like. It is used and can be used in these technical fields.
In the present specification, acrylate and / or methacrylate is represented by (meth) acrylate, acryloyl group and / or methacryloyl group is represented by (meth) acryloyl group, and acrylic acid and / or methacrylic acid is represented by (meth) acrylic acid. .
In the following description, unless otherwise specified, a plastic film or sheet is collectively expressed as “plastic film or the like”, and a film or sheet is collectively expressed as “film or the like”.

Conventionally, in a laminating method in which a thin-layer adherend such as a plastic film or a thin-layer adherend such as a plastic film and a thin-layer adherend made of another material are bonded together, an ethylene-vinyl acetate copolymer is used. A solvent-type adhesive composition containing a polymer or a polyurethane-based polymer is applied to the first thin-layer adherend and dried, and then the second thin-layer adherend is applied to the first thin-layer adherend using a nip roller or the like. The dry laminating method for pressure bonding is mainly performed.
The adhesive composition used in this method generally contains a large amount of a solvent in order to make the coating amount of the composition uniform, but for this reason, a large amount of solvent vapor is volatilized during drying, resulting in toxicity, work safety and Environmental pollution is a problem. In addition, the adhesive composition is a thin layer in a post-processing step such as a heat seal for bonding the obtained laminate film and a ruled line step for engraving grooves immediately after the thin layer adherend is bonded. There is a problem that the adherends are separated from each other.
As an adhesive composition for solving these problems, a solventless adhesive composition has been studied.

As the solventless adhesive composition, a two-component adhesive composition and an adhesive composition that is cured by an active energy ray such as an ultraviolet ray or an electron beam are widely used.
As the two-component adhesive composition, a so-called polyurethane adhesive composition is mainly used in which a polymer having a hydroxyl group at the terminal is a main agent and a polyisocyanate compound having an isocyanate group at the terminal is a curing agent. However, the composition has a drawback that it takes a long time to cure, and thus there is a problem in productivity such as being unable to enter a post-processing step such as a ruled line step immediately after laminating the thin layer adherend. .
On the other hand, the active energy ray-curable adhesive composition is excellent in productivity because of its high curing rate, and has recently attracted attention.

On the other hand, liquid crystal display devices are widely used in navigation systems for automobiles, small electronic devices such as mobile phones and PDAs, screens of word processors and personal computers, and even television receivers because of their features such as thinness, light weight, and low power consumption. doing.
In recent years, an active energy ray-curable adhesive has been used for bonding various optical films and the like used in the liquid crystal display element.

  Examples of the optical film include a polarizing plate, a retardation film, a viewing angle compensation film, a brightness enhancement film, an antireflection film, an antiglare film, a lens sheet, and a diffusion sheet, and various types of plastics are used. It has been.

  For example, for polarizing plates, polyvinyl alcohol is used as a polarizer, and triacetyl cellulose is used as a protective film for the polarizer. Examples of the retardation film include cycloolefin polymers such as norbornene resin, and polyesters such as polyethylene terephthalate (PET) are used for various applications including a brightness enhancement film.

  As active energy ray-curable adhesive compositions for polarizing plates, compositions using photo radical polymerization, compositions using photo cation polymerization, and compositions using both photo radical polymerization and photo cation polymerization are known. Yes.

As an active energy ray-curable adhesive composition using photo radical polymerization, a composition containing a radical polymerizable compound containing a hydroxyl group and the like and a radical polymerizable compound not containing a polar group in a specific ratio (Patent Document 1), etc. It has been known.
However, the composition has a large shrinkage during curing, and depending on the type of adherend, it has been difficult to obtain sufficient peel strength due to the generation of stress at the interface.
Moreover, in order to solve this problem, the composition containing urethane (meth) acrylate and an acrylamide derivative is examined (for example, patent document 2 etc.).
However, the composition has a problem that water resistance and heat-and-moisture resistance that are practically required are insufficient although the initial adhesive force to the hydrophilic plastic is high. It is also possible to reduce the shrinkage stress during curing by improving the flexibility of the adhesive composition. However, since such a means lowers the heat resistance and water resistance of the adhesive, There is a problem that defects such as peeling, foaming, and cracks occur in applications that require high performance.

Examples of the active energy ray-curable adhesive composition using cationic photopolymerization include a composition mainly composed of an epoxy resin containing no aromatic ring (Patent Document 3), an aliphatic epoxy, an alicyclic epoxy, and / or A composition containing oxetane (Patent Document 4) and the like are known.
The composition has an advantage in that the generation of stress at the interface can be suppressed because the shrinkage at the time of curing is relatively small compared to the composition using photo radical polymerization.
However, photocationic polymerization is generally known to cause polymerization inhibition due to moisture and basic substances. In high humidity environments, substrates with a lot of moisture, and substrates with a basic surface. It was difficult to obtain sufficient peel strength. In addition, by using a composition containing a polyfunctional epoxy resin as a main component, it is possible to reduce the effect of curability reduction due to polymerization inhibition. There is a problem that the stress between the substrate and the base material becomes high and the adhesive force becomes insufficient.

  The active energy ray-curable adhesive composition using both photoradical polymerization and photocationic polymerization includes (meth) acrylate having an isocyanuric ring skeleton, alicyclic epoxy compound, a compound containing a hydroxyl group, and a photoacid generator. Composition (Patent Document 5) An epoxy resin having two or more epoxy groups, at least one of which is an alicyclic epoxy group, having two or more epoxy groups and an alicyclic epoxy Composition having an epoxy resin having no group, a cationic photopolymerization initiator and a polymerizable monomer (Patent Document 6), a compound having two or more (meth) acryl groups, a hydroxyl group and one (meth) acryl group Known is a compound, a cationic polymerizable compound having a (meth) acrylic group, a radical photopolymerization initiator and a composition containing a cationic photopolymerization initiator (Patent Document 7). That.

  These compositions are intended to solve the problem of shrinkage during curing and polymerization inhibition due to moisture by hybridization, but according to the study by the present inventors, it has been found that there are the following problems. .

  The composition disclosed in Patent Document 5 contains a (meth) acrylate compound having an isocyanuric ring skeleton as an essential component, but according to the study by the present inventors, a bifunctional photoradically polymerizable compound is composed. When it is contained in a large amount, the shrinkage at the time of curing is not so small and stress generation at the interface cannot be suppressed. For this reason, it has been found that it is difficult to obtain sufficient peel strength depending on the substrate. .

  The composition disclosed in Patent Document 6 is described in the specification to include a hybridized composition as a concept, but in the examples, the composition is composed only of a photocationically polymerizable monomer. Only the thing is shown and lacks concreteness.

  The composition disclosed in Patent Document 7 contains a cationically polymerizable compound having a (meth) acrylic group as an essential component at a specific ratio, but according to the study by the present inventors, the compound is contained in the composition. If it is contained in a large amount, the shrinkage at the time of curing is not so small and the generation of stress at the interface cannot be suppressed, and it has been found that it is difficult to obtain a sufficient peel strength depending on the substrate.

JP 2008-009329 A (Claims) JP 2007-177169 A (Claims) JP-A-2004-245925 (Claims) JP 2008-134384 A (Claims) JP 2008-233279 A (Claims) JP 2008-257199 A (Claims) JP 2008-260879 A (Claims)

In various plastic films used in the above-described applications, particularly, adhesion to PET films that are difficult to adhere even if the film surface is corona-treated, difficult-to-adhere plastic films such as cycloolefin polymer films is required. . Furthermore, when used in applications that require strict durability, performance that does not deteriorate the adhesion performance is often required, especially even under high humidity and high temperature conditions.
The present invention has been made in view of the above problems, and is an active energy ray-curable adhesive composition that is excellent in adhesion to hardly-adhesive plastic films and the like and does not deteriorate even under high humidity and high temperature conditions. The purpose is to provide goods.

As a result of various studies to solve the above problems, the present inventors have made urethane (meth) acrylate, an ethylenically unsaturated group-containing compound having a hydroxyl group, another ethylenically unsaturated group-containing compound, polyisocyanate, and thermal polymerization. The active energy ray-curable adhesive composition containing an initiator has excellent adhesion to various plastic films and the like, particularly difficult-to-adhere plastic films such as PET films and cycloolefin polymer films, and ultraviolet absorbers It can be suitably used even for substrates that are extremely difficult to transmit ultraviolet rays, which are typical active energy rays, including pigments, etc., and even in applications where severe durability is required, especially under high humidity and high temperature conditions The present invention was completed by finding that it has sufficient performance.
Hereinafter, the present invention will be described in detail.

  The composition of the present invention can maintain a high adhesive force even under high-temperature and high-humidity conditions for various plastic films, particularly difficult-to-adhere plastic films, and is a thin-layer adherend such as various plastic films. In particular, it can be suitably used for the production of optical films used for liquid crystal display devices, solar cells and the like.

The present invention relates to an active energy ray-curable adhesive composition for plastic films or sheets containing the following components (A) to (E) in the following proportions.
(A) Urethane (meth) acrylate , which is a compound obtained by reacting a polyol and an organic polyisocyanate reaction product with a hydroxyl group-containing (meth) acrylate (hereinafter referred to as “component (A)”): (A) to (C) 10 to 70% by weight in the total amount of the components (hereinafter referred to as “curable components”)
(B) Compound having a hydroxyl group and one ethylenically unsaturated group in the molecule [hereinafter referred to as “component (B)”]: 3 to 40% by weight in the curable component
(C) Ethylenically unsaturated group-containing compound other than components (A) and (B) [hereinafter referred to as “component (C)”]: 27 to 65% by weight in the total amount of the curable component
(D) Polyisocyanate [hereinafter referred to as “component (D)”]: 1 to 20% by weight based on the total amount of curable components
(E) Thermal polymerization initiator [hereinafter referred to as “component (E)”]: 0.001 to 10% by weight based on the total amount of the curable components
In addition, in this invention, a sclerosing | hardenable component means the said (A)-(C) component and is a compound which has an ethylenically unsaturated group, and means the component hardened | cured by irradiation of an active energy ray.
Hereinafter, the essential components (A) to (E) will be described.

1. (A) Component (A) A component is urethane (meth) acrylate. In this invention, by containing (A) component, the hardened | cured material obtained will be excellent in adhesive force in any conditions of high temperature or high humidity.
As the component (A), both oligomers and polymers can be used, and those having a weight average molecular weight of 500 to 50,000 are preferable, and those having a weight average molecular weight of 3,000 to 40,000 are more preferable.
In the present invention, the weight average molecular weight is a value obtained by converting the molecular weight measured by gel permeation chromatography into polystyrene.

The component (A), Po triol, Ru reactant der organic polyisocyanates and hydroxyl group-containing (meth) acrylate. Furthermore, as the component (A), a compound obtained by reacting a reaction product of a polyol and an organic polyisocyanate with a hydroxyl group-containing (meth) acrylate is preferable.

As the polyol, a polyol having a polyether skeleton, a polyester skeleton or a polycarbonate skeleton is preferable.
The component (A) is preferably a urethane (meth) acrylate having two (meth) acryloyl groups (hereinafter referred to as a bifunctional urethane (meth) acrylate), a polyether skeleton, a polyester skeleton or a polycarbonate. Bifunctional urethane (meth) acrylate which is a reaction product of a diol having a skeleton, an organic diisocyanate and a hydroxyl group-containing (meth) acrylate is more preferable, and a reaction product of a diol having a polyether skeleton, a polyester skeleton or a polycarbonate skeleton and an organic diisocyanate. Particularly preferred is a bifunctional urethane (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylate.

Here, examples of the diol having a polyether skeleton include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol.
Examples of the polyol having a polyester skeleton include an esterification reaction product of a diol such as a low molecular weight diol or polycaprolactone diol and an acid component such as a dibasic acid or an anhydride thereof.
Examples of the low molecular weight diol include ethylene glycol, propylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol and 1,6-hexanediol.
Examples of the dibasic acid or an anhydride thereof include adipic acid, succinic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid and terephthalic acid, and anhydrides thereof.
Examples of the polycarbonate polyol include a reaction product of the low molecular weight diol or / and bisphenol such as bisphenol A and a carbonic acid dialkyl ester such as ethylene carbonate and carbonic acid dibutyl ester.

  Organic polyisocyanates include tolylene diisocyanate, 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, 1,6-hexane diisocyanate trimer, hydrogenated tolylene diisocyanate, hydrogenated 4 , 4'-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, paraphenylene diisocyanate, tolylene diisocyanate dimer, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate interadduct, 4,4'-dicyclohexylmethane diisocyanate , Trimethylolpropane tris (tolylene diisocyanate) adduct, isophorone diisocyanate and the like. The organic polyisocyanate is preferably an organic diisocyanate.

  As the hydroxyl group-containing (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, hydroxypentyl (meth) acrylate, hydroxyhexyl (meth) acrylate, hydroxyoctyl And hydroxyalkyl (meth) acrylates such as (meth) acrylate, pentaerythritol tri, di- or mono (meth) acrylate, and trimethylolpropane di- or mono (meth) acrylate.

(A) A component may be manufactured according to the conventional method.
For example, after an addition reaction between a polyol and an organic isocyanate to produce an isocyanate group-containing compound, this is reacted with a hydroxyalkyl (meth) acrylate, and a polyol, an organic isocyanate and a hydroxyalkyl (meth) acrylate are reacted simultaneously. Methods and the like.
A catalyst for urethanization can be added to these reactions. Specific examples include tin compounds such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dioctate and dibutyltin diacetylacetonate, bismuth compounds such as bismuth dioctate, and calcium compounds such as calcium dioctate.
These reactions can be carried out without solvent or in the presence of a solvent.

  As the component (A), an ester is particularly excellent in that the adhesive strength under high humidity is excellent, and the adhesive strength after curing is small due to a change in viscosity of the composition over time or a change in viscosity. Urethane acrylates using polyether glycols such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol and the like that have no bond are preferred.

As the component (A), only one type of the above-described compounds may be used, or two or more types may be used in combination.
(A) The ratio of a component is 10 to 70 weight% in the total amount of a sclerosing | hardenable component, Preferably it is 20 to 60 weight%. If the proportion of the component (A) is less than 10% by weight, the heat resistance and water resistance of the cured product will be insufficient, and if it exceeds 70% by weight, the viscosity of the composition will increase and the coatability will increase. Decreases, or the adhesive strength of the cured product becomes insufficient.

2. Component (B) The component (B) is a compound having a hydroxyl group and one ethylenically unsaturated group in the molecule.
The component (B) can be used in combination with the component (D) described later, and can particularly improve the adhesive strength particularly at high temperatures and high humidity. The reason for this is that in the cross-linked product consisting of only the components (A) and (C), the cross-linking point is via an ester bond, and the ester bond breaks when exposed to high temperature and high humidity. In contrast, the adhesive composition of the present invention also includes a crosslinking point through a urethane bond, so that a strong adhesive layer can be retained even when the ester bond is broken. It is considered a thing.
In addition, in the adhesion of hard-to-adhere plastics, corona treatment of hard-to-adhesive plastics is generally performed, but it is assumed that a reaction in which polar groups generated on the plastic surface bind to isocyanate is also caused by corona treatment. Yes.

Examples of the ethylenically unsaturated group in component (B) include a vinyl group and a (meth) acryloyl group, and a (meth) acryloyl group is preferred.
Specific examples of the compound having a hydroxyl group and a (meth) acryloyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and hydroxypentyl (meth) acrylate. Hydroxyalkyl (meth) acrylates such as hydroxyhexyl (meth) acrylate and hydroxyoctyl (meth) acrylate;
Polyol mono (meth) acrylates containing hydroxyl groups such as pentaerythritol mono (meth) acrylate and trimethylolpropane mono (meth) acrylate;
N-hydroxyalkyl (meth) acrylamides such as N-hydroxyethyl (meth) acrylamide and N-hydroxypropyl (meth) acrylamide; and hydroxyalkyl vinyl ethers such as hydroxyethyl vinyl ether, hydroxypropyl vinyl ether and hydroxybutyl vinyl ether, and the like.
Furthermore, as (B) component, the compound which has one hydroxyl group and one ethylenically unsaturated group in a molecule | numerator is preferable, and a hydroxyalkyl (meth) acrylate is more preferable.

As the component (B), only one type of the above-described compounds may be used, or two or more types may be used in combination.
(B) The ratio of a component is 3 to 40 weight% in the total amount of a sclerosing | hardenable component, Preferably it is 5 to 30 weight%. When the proportion of the component (B) is less than 3% by weight, the adhesive strength is insufficient, and when it exceeds 30% by weight, the moisture and heat resistance and water resistance of the cured product are insufficient.

3. Component (C) Component (C) is an ethylenically unsaturated group-containing compound other than components (A) and (B), and any ethylenically unsaturated compound other than components (A) and (B) Compounds can be used.
As the component (C), various compounds can be used as long as the compound contains an ethylenically unsaturated group, and examples thereof include vinyl compounds and compounds having a (meth) acryloyl group, and compounds having a (meth) acryloyl group. preferable.

Examples of the compound having a (meth) acryloyl group include (meth) acrylamide compounds and (meth) acrylates.
Examples of the (meth) acrylamide compound include compounds having one (meth) acrylamide group. Specifically, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, t-octyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N -Dimethylaminopropyl (meth) acrylamide, (meth) acryloylmorpholine, acrylamide-2-methylpropanesulfonic acid, N-isopropyl (meth) acrylamide and the like.

  Specific examples of (meth) acrylate include (meth) acrylate having one (meth) acryloyl group (hereinafter referred to as “monofunctional (meth) acrylate”) and two or more (meth) acryloyl groups ( (Meth) acrylate (hereinafter referred to as “polyfunctional (meth) acrylate”).

Monofunctional (meth) acrylates include alkyl (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl acrylate and lauryl acrylate;
Monofunctional (meth) acrylates having aromatic groups such as phenoxyethyl (meth) acrylate and benzyl (meth) acrylate;
Monofunctional (meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate;
Monofunctional (meth) acrylates having an alicyclic group such as isobornyl (meth) acrylate and dicyclopentadienyl (meth) acrylate;
Monofunctional (meth) acrylates having alkoxyalkyl groups such as ethyl carbitol (meth) acrylate and alkyl carbitol (meth) acrylate such as 2-ethylhexyl carbitol (meth) acrylate;
Examples thereof include glycidyl (meth) acrylate; and (meth) acrylate having a maleimide group such as (meth) acrylolyloxyethyl hexahydrophthalimide.

In the polyfunctional (meth) acrylate, as the bifunctional (meth) acrylate, 1,6-hexanediol di (meth) acrylate, nonanediol di (meth) acrylate, polyethylene glycol di (meth) acrylate, ethylene glycol di (meth) ) Acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, and the like.
Trifunctional or higher (meth) acrylates include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( And (meth) acrylate and tris (2- (meth) acryloyloxyethyl) isocyanurate.
As polyfunctional (meth) acrylate, an oligomer can also be used and epoxy poly (meth) acrylate and polyester (meth) acrylate are mentioned.

  Examples of the vinyl compound include N-vinylcaprolactam, N-vinylcarbazole, and vinylnaphthalene.

As the component (C), among the above-mentioned compounds, those in which stress does not easily accumulate at the substrate interface are preferable, and (meth) acrylamide compounds, monofunctional (meth) acrylates, and polyfunctional (meth) acrylates having a large acrylic equivalent are preferable. .
Furthermore, tetrahydrofurfuryl (meth) acrylate is preferable as the (meth) acrylamide compound or monofunctional (meth) acrylate in terms of high plastic erodibility.
A low Tg (meth) acrylate having an alkyl difference of 4 to 12 carbon atoms is also preferable. Specifically, the carbon number of butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, etc. Examples thereof include 4 to 12 alkyl (meth) acrylates, and carbitol (meth) acrylates having an alkyl group having 1 to 12 carbon atoms such as ethyl carbitol (meth) acrylate and 2-ethylhexyl carbitol (meth) acrylate. It is done.
Furthermore, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, and dicyclopentanyl (meth) in that the cured product has excellent water resistance and heat resistance. (Meth) acrylate, benzyl (meth) acrylate, etc. which have alicyclic skeletons, such as an acrylate, are mentioned.
The compound particularly preferable as the component (C) is one or more selected from the group consisting of an acrylamide compound, a carbitol (meth) acrylate having an alkyl group having 1 to 12 carbon atoms, and a (meth) acrylate having an alicyclic skeleton. is there.

As the component (C), only one type of the above-described compounds may be used, or two or more types may be used in combination.
(C) The content rate of a component is 27 to 65 weight% in the total amount of a sclerosing | hardenable component, Preferably it is 35 to 60 weight%. If the proportion of the component (C) is less than 27% by weight, sufficient moisture and heat resistance cannot be obtained, and if it exceeds 65% by weight, the adhesive strength is lowered, or the glass transition depends on the application. Secondary performance such as temperature, water permeability, water absorption, etc. cannot be adjusted.

4). Component (D) Component (D) is a polyisocyanate compound. After the adhesive composition is irradiated with active energy rays and an adhesive layer is formed, component (D) is further changed to component (B). By reacting with a hydroxyl group, the heat resistance and heat-and-moisture resistance can be greatly improved. This component is a component necessary for maintaining a strong adhesive layer even when the ester bond of a crosslinked product made of (meth) acrylate is cleaved under severe high temperature and high humidity conditions. It is necessary to have a plurality of isocyanates therein.

As the component (D), various polyisocyanates can be used.
Specifically, tolylene diisocyanate, 1,6-hexane diisocyanate, 4,4′-diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, 1,6-hexane diisocyanate trimer, hydrogenated tolylene diisocyanate, hydrogenated 4, 4′-diphenylmethane diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate, paraphenylene diisocyanate, tolylene diisocyanate dimer, 1,5-naphthalene diisocyanate, hexamethylene diisocyanate interadduct, 4,4′-dicyclohexylmethane diisocyanate, Examples include trimethylolpropane tris (tolylene diisocyanate) adduct and isophorone diisocyanate. The organic polyisocyanate is preferably an organic diisocyanate.
Examples of commercially available products include Nippon Polyurethane Co., Ltd. Coronate L, Coronate T-65, Coronate T-80, Coronate T-100, Millionate MT, Millionate MR, etc., and Dura from Asahi Kasei Chemicals Corporation. Nate series, TPA-100, TKA-100, MFA-75B, MHG-80B, TLA-100, TSA-100, TSS-100, TSE-100, 24A-100, etc. can be mentioned.

  As the component (D), when a composition that is reacted at a low temperature for a shorter time is preferable, a compound having an aromatic isocyanate group is preferable, and tolylene diisocyanate, xylylene diisocyanate, and tolylene diisocyanate dimer are preferable. . In addition, although a reaction takes time, when a composition with little coloration after long-term outdoor exposure is preferable, a compound having an aliphatic isocyanate group is preferable, and 1,6-hexane diisocyanate, 1,6-hexane diisocyanate trimer And isophorone diisocyanate are preferred. In particular, when weather resistance is important, 1,6-hexane diisocyanate trimer is particularly preferable.

  The content rate of (D) component is 1-20 weight% with respect to the total amount of a sclerosing | hardenable component, Preferably it is 3-10 weight%. When the content ratio of the component (D) is less than 1% by weight, the heat resistance and moist heat resistance of the adhesive layer becomes insufficient, and when it exceeds 20% by weight, the strain of crosslinking by the component (D) is practically sufficient. It cannot be reduced to the level, and warping of the film occurs.

5. Component (E) The component (E) is a thermal polymerization initiator that decomposes by heating to generate radicals.
By including the component (E), after applying the composition to the substrate, it is possible to improve the adhesion to the substrate when irradiated with active energy rays and further heated.
When the substrate to be used is a material that is difficult to transmit active energy rays, for example, when the plastic film or sheet used as the substrate contains an ultraviolet absorber or / and a pigment, the composition is applied to the substrate. Even if the active energy rays are irradiated after pasting, it may not be cured until sufficient adhesive strength is developed. (E) By including a component, after coating a composition to such a base material, after bonding another base material, irradiating an active energy ray, and heating, the hydroxyl group of (B) component And the component (D) not only react, but the laminate can be more firmly bonded by reacting the unreacted ethylenically unsaturated groups of the components (A) to (C). In particular, the composition of the present invention, as described later, was applied to the substrate, then irradiated with active energy rays, and the adhesive layer was thickened in a semi-cured state to form a syrup. Later, even when using the manufacturing method of the laminated body which bonds and heats the base material, the base materials can be firmly bonded to each other by the same action.

Examples of the component (E) include organic peroxides and azo compounds.
Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl- , 5-di (m-toluoylperoxy) hexane, t-butylperoxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5 -Di (benzoylperoxy) hexane, t-butylperoxyacetate, 2,2-bis (t-butylperoxy) butane, t-butylperoxybenzoate, n-butyl-4,4-bis (t-butyl) Peroxy) valerate, di-t-butylperoxyisophthalate, α, α′-bis (t-butylperoxy) diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t- Butylperoxy) hexane, t-butylcumyl peroxide, di-t-butylperoxide P-menthane hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 Examples include 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, and t-butyl hydroperoxide.

  Specific examples of the azo compound include 1,1′-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. Azodi-t-octane and azodi-t-butane.

These may be used alone or in combination of two or more. Further, the organic peroxide can be used as a redox catalyst by combining with a reducing agent.
As the component (E), an organic peroxide is preferable because no bubbles are generated in the resulting resin sheet.

  (E) The content rate of a component is 0.001 to 10 weight% with respect to the total amount of a sclerosing | hardenable component, Preferably it is 0.1 to 5 weight%. If the content ratio of the component (E) is less than 0.001% by weight, polymerization of the curable component becomes insufficient, and sufficient adhesive strength cannot be obtained, and odor due to unreacted components may be a problem. Yes, if it exceeds 10% by weight, the polymerization proceeds rapidly due to heating, which may cause deformation of the film or the like.

6). Other components The composition of the present invention comprises the components (A) to (E) as essential components, but various components can be blended depending on the purpose.
When the composition of the present invention is cured by ultraviolet rays or visible rays, a photopolymerization initiator [hereinafter referred to as “component (F)”] can be blended. In addition, in the case of applications that are used outdoors, such as automobile applications and solar cell applications, antioxidants, ultraviolet absorbers, and light are used to maintain sufficient durability over long periods of time against outdoor heat and light. A stabilizer, a silane coupling agent [hereinafter referred to as “component (G)”] and the like can be blended. For the purpose of improving moisture curability, a moisture curing catalyst (hereinafter referred to as “component (H)”) may be blended.
Hereinafter, each component will be specifically described.

6-1. Component (F) The component (F) is a radical photopolymerization initiator.
Component (F) is a compound that generates radicals upon irradiation with active energy rays and initiates polymerization of a compound having an ethylenically unsaturated group. When an electron beam is used as the active energy ray, it is not necessary to add the component (F).

Specific examples of the component (F) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, oligo [2-hydroxy-2-methyl-1- [4-1- (methylvinyl) ) Phenyl] propanone, 2-hydroxy-1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] -phenyl] -2-methylpropan-1-one, 2-methyl-1- [4 -(Methylthio)] phenyl] -2-morpholinopropane-1-o 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin-4-yl-phenyl) -Aromatic ketone compounds such as butane-1-one, Adekaoptomer N-1414 (manufactured by Asahi Denka), phenylglyoxylic acid methyl ester, ethyl anthraquinone and phenanthrenequinone;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4- (methylphenylthio) phenylphenylmethane, methyl-2-benzophenone, 1- [4- (4-Benzoylphenylsulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfonyl) propan-1-one, 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis ( Benzophenone compounds such as diethylamino) benzophenone, N, N′-tetramethyl-4,4′-diaminobenzophenone, N, N′-tetraethyl-4,4′-diaminobenzophenone and 4-methoxy-4′-dimethylaminobenzophenone ;
Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate and bis (2,6 -Acylphosphine oxide compounds such as -dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3- [3,4-dimethyl-9-oxo-9H-thioxanthone-2-yl] oxy] -2-hydroxy Examples thereof include thioxanthone compounds such as propyl-N, N, N-trimethylammonium chloride and fluorothioxanthone.

  Any compound can be suitably used by adjusting the blending amount and active energy ray irradiation conditions, but since the film is pasted after the active energy ray irradiation, the surface tack at the air interface of the semi-cured adhesive layer is reduced. Larger ones tend to have better adhesive strength. From this, it is generally considered that a material that is relatively susceptible to oxygen inhibition and is slightly inferior in surface curability is easy to handle. From this point of view, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl- (2,4,6-trimethylbenzoyl) phenylphosphinate And acylphosphine oxide compounds such as bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide are preferable.

As the component (F), the above-described compounds may be used alone, or two or more kinds may be used.
The proportion of component (F) is 0.1 to 20% by weight, preferably 1 to 10% by weight, based on the total amount of curable components. (F) By making the ratio of a component 0.1 weight% or more, photocurability of a composition can be made sufficient and adhesiveness can be improved, and by making it into 20 weight% or less, it is the adhesive layer. The adhesiveness can be improved by preventing deterioration of internal curability.

6-2. Component (G) The component (G) is a silane coupling agent that can improve the interfacial adhesive strength between the adhesive layer and the hydrophilic plastic. The silane coupling agent used in the present invention is not particularly limited as long as it can contribute to improvement in adhesion to the substrate.

  Specific examples of the component (G) include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3- Glycidoxypropyltriethoxysilane, 3- (meth) acryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- (meth) acryloxypropylmethyldiethoxysilane, 3- (meth) acryloxypropyl Triethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-amino Propyltriethoxysilane, 3-aminopropyltrimethoxy Lan, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1,3-dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, Examples include 3-mercaptopropyltrimethoxysilane.

As the component (G), only one kind of the above-described compounds may be used, or two or more kinds may be used.
(G) As for the usage rate when using a component, 0.1-10 weight% is preferable in a composition, More preferably, it is 1-5 weight%.
By making the use ratio of the component (G) 0.1% by weight or more, the adhesive force of the composition can be improved, and by making it 10% by weight or less, it is possible to prevent the adhesive force from changing over time. it can.

6-3. Component (H) The component (H) is a moisture curing catalyst.
As the component (H), various compounds can be used as long as they are used in a conventional moisture-curable composition and can react the component (D) with moisture.
Specific examples of the component (G) include organometallic compounds and tertiary amines.

Examples of organometallic compounds include organotin compounds, organoiron compounds, organozinc compounds, organotitanium compounds, organoaluminum compounds, organozirconium compounds, and organobismuth compounds.
Examples of organic tin compounds include dibutyltin dilaurate, dibutyltin maleate, dibutyltin diacetate, dibutyltin diacetacetonate, tin octylate, tin naphthenate, tin laurate and tin ferzatic acid, and tin carboxylates Examples include a reaction product of dibutyltin oxide and phthalate ester.
Examples of the organic titanium compound include titanic acid esters such as tetrabutyl titanate and tetrapropyl titanate, and titanium chelate compounds such as titanium tetraacetylacetonate.
Examples of the organoaluminum compound include aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate and the like.
Examples of the organic zirconium compound include zirconium chelate compounds such as zirconium tetraacetylacetonate.
Examples of the organic bismuth compound include bismuth-tris (neodecanoate), bismuth-tris (2-ethylhexoate), and bismuth octylate.
Organic iron compounds and organic zinc compounds are preferred compounds and will be described in detail later.

Tertiary amine compounds include trialkylamines such as triethylamine; tetraalkylalkylenediamines such as tetramethylethylenediamine and tetramethylhexanediamine; pentaalkyldialkylenetriamines such as pentamethyldiethylenetriamine; trimethylaminoethylpiperazine and methylhydroxyethylpiperazine Piperazines; dialkylaminoalkyl alcohols such as dimethylaminoethoxyethanol; trialkylaminoalkyl alcohols of trimethylaminoethylethanolamine; N-alkylimidazoles such as 1,2-dimethylimidazole; bis (dimethylaminoethyl) ether; 1,4-diazabicyclo [2,2,2] octane (DABCO)]; and 2,4,6 -Tertiary amines such as tris (dimethylaminomethyl) phenol.
Examples other than these include N-methylmorpholine and 1,8-diazabicyclo [5,4,0] undecene-7 (DBU).

In the present invention, the metal component derived from the urethanization catalyst contained in the component (A) can be reduced, and the insulation reliability of the composition is excellent. Therefore, as the component (H), an organic iron compound and Organic zinc compounds are preferred, and those produced using a metal compound represented by the following general formula (1) as a catalyst are more preferred.
M (X) _n (1)
[In Formula (1), M represents Fe or Zn, X is the same or different and represents a β-diketone, a halogen atom, an acyloxy group, or an alkoxy group, and n represents an integer of 2 or 3. ]

M represents Fe or Zn, and Fe is preferable in that it is superior in catalytic activity.
Examples of the β-diketone represented by X include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2-methylhexane-3,5-dione, and 6-methylheptane-2,4-dione. 2,6-dimethylheptane-3,5-dione, 4,6-nonanedione, 2,8-dimethylnonane-4,6-dione, 2,2,6,6-tetramethylheptane-3,5-dione , Tridecane-6,8-dione, methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate, methyl propionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, propionyl tert-butyl and hexafluoroacetylacetone Among these, acetylacetone is inexpensive and urethanized The preferred because it is excellent in the activity of the response.
Examples of the halogen atom represented by X include a chlorine atom and a bromine atom, and a chlorine atom is preferable.
As the acyloxy group represented by X, for example, an acyloxy group having 3 to 20 carbon atoms is preferable. Specifically, a pentanoyl group, a hexanoyl group, a 2-ethylhexanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, A dodecanoyl group, an octadecanoyl group, etc. are mentioned.
As the alkoxy group represented by X, for example, an alkoxy group having 1 to 10 carbon atoms is preferable, and examples thereof include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, a butoxy group, and a 2-ethylhexyloxy group. be able to.
X may be any one of the above, or a combination of two or more.
Among these, as X, a functional group other than a halogen atom is preferable in that the electrical properties of the cured product are particularly excellent, acetylacetone and hexafluoroacetylacetone are more preferable, and solubility in a reaction solution and a composition is improved. From the viewpoint of superiority, acetylacetone is particularly preferable.

Among these, an iron β-diketone complex represented by the following formula (2) is preferable because it is particularly excellent in the reactivity of the urethanization reaction.
Fe (X ′) ₃ (2)
[In Formula (2), X ′ represents a β-diketone. ]
As the β-diketone represented by X ′, the β-diketone represented by the above X can be selected.

  N representing the number of X is an integer of 2 or 3, and since production stability is good, n is 3 when M is Fe, and n is 2 when M is Zn.

  As specific examples of the metal compound, when X is a β-diketone, for example, tris (acetylacetonato) iron, tris (2,2,6,6-tetramethyl-3,5-heptanedionate) iron , Tris (tetrafluoroacetylacetonate) iron, bis (acetylacetonato) zinc, bis (2,2,6,6-tetramethyl-3,5-heptanedionate) zinc, bis (tetrafluoroacetylacetonate) Zinc etc. are mentioned. When X is a halogen atom, for example, ferric chloride and zinc chloride are exemplified. When X is an acyloxy group, for example, tris (2-ethylhexanoic acid) iron, iron naphthenate, bis (2-ethylhexanoic acid) zinc, zinc naphthenate and the like can be mentioned. When X is an alkoxy group, for example, triethoxy iron, triisopropoxy iron, diethoxy zinc, diisopropoxy zinc and the like can be mentioned.

  Among these, those in which M is Fe and n is 3 are more preferable because of excellent catalytic activity in the urethanization reaction. Specific examples include tris (acetylacetonato) iron and ferric chloride. Tris (acetylacetonato) iron represented by the formula (2) is particularly preferable because of its excellent catalytic activity.

  As the component (H), an organic tin compound, an organic iron compound, and a tertiary amine are preferable in terms of excellent curability.

As the component (H), the above compounds may be used alone or in combination of two or more.
The blending ratio of the component (H) is preferably 5% by weight or less, more preferably 0.05 to 3% by weight in the composition.
By adding the component (H), the moisture curing time can be shortened. On the other hand, when the content is 5% by weight or less, the storage stability of the composition can be improved.

6-4. Other components In addition to the above, other components usually used in adhesive compositions can be blended with the composition of the present invention.

Examples of additives for improving durability include phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, and the like.
Examples of the phenolic antioxidant include hindered phenols such as di-t-butylhydroxytoluene. As what is marketed, Ade-20 Co., Ltd. AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80 etc. are mentioned.
Examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphites and triaryl phosphites. Examples of commercially available products of these derivatives include Adeka Co., Ltd., ADK STAB PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. Etc.
Examples of sulfur-based antioxidants include thioether compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by Adeka Corporation.
These may be used alone or in combination of two or more. Preferred combinations of these antioxidants include the combined use of phenolic antioxidants and phosphorus antioxidants, and the combined use of phenolic antioxidants and sulfurous antioxidants.
The use ratio when using the antioxidant is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight in the composition.
When the use ratio is 0.1% by weight or more, the durability of the composition can be improved, and when it is 5% by weight or less, insufficient curing and insufficient adhesive strength can be prevented.

For the purpose of improving light resistance, an ultraviolet absorber may be used. Triazine-based ultraviolet absorbers such as Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 479 manufactured by BASF Corporation, Tinuvin 900, Tinuvin 928, Tinuvin 1130 Benzotriazole-based UV absorbers such as
These may be used alone or in combination of two or more.
The use ratio when using the ultraviolet absorber is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight in the composition. By setting the content to 5% by weight or less, it is possible to prevent the curability of the composition from decreasing.

7). Active energy ray-curable adhesive composition for plastic film or sheet The composition of the present invention essentially comprises the components (A) to (E).
As a manufacturing method of a composition, it can manufacture by stirring and mixing the said (A)-(E) component and another component as needed according to a conventional method.
In this case, heating can be performed as necessary. The heating temperature may be appropriately set according to the composition to be used, the substrate, the purpose, etc., but is preferably 30 to 80 ° C. However, the reaction of the component (D) slowly proceeds by mixing with the component (B), and the component (E) may generate radicals by heating to cause polymerization of ethylenically unsaturated bonds. It is preferable to mix components (D) and components other than (E), add component (D) and (E) immediately before coating, and stir and mix at 40 ° C. or less as much as possible. In addition, it is preferable that the component (D) is used up as soon as possible after compounding.
The viscosity of the composition of the present invention may be appropriately set according to the purpose, but the viscosity of the mixture excluding the component (D) is preferably 100 to 5,000 mPa · s, more preferably 300 to 4,000 mPa · s. s.

The composition of the present invention can be used for adhesion between plastic films and the like, and adhesion between plastic films and the like and various other substrates (hereinafter referred to as other substrates).
In the following, when simply described as “base material”, it means a general term for plastic films and other base materials.
Other base materials include plastic that is not film or sheet (hereinafter referred to as “non-film plastic”), paper, metal, and the like.

Examples of materials for plastic films include chlorine-based resins such as polyvinyl chloride and polyvinylidene chloride; cellulose-based resins such as cellulose and triacetyl cellulose; polyolefins such as polyethylene and polypropylene; polystyrenes; ABS resins; polyamides; Polyester; Polycarbonate; Polyurethane; Polyvinyl alcohol; Cycloolefin polymer such as norbornene resin; Polymethyl methacrylate; Acrylic / styrene resin; Ethylene-vinyl acetate copolymer; and chlorinated polypropylene.
Among these, the composition of the present invention can be preferably applied to a plastic film or the like that is particularly difficult to adhere. Specific examples include polyolefins, polyesters, cycloolefin polymers, and ethylene-vinyl acetate copolymers.
As a film thickness of a plastic film or the like, various film thicknesses can be used according to the purpose, and 5 to 100 μm is preferable.
Examples of the non-film plastic material include the same materials as described above. The substrate used in the present invention does not need to be transparent, and does not transmit ultraviolet rays, such as a film containing an ultraviolet absorbent, a film containing a pigment, a copper foil, a metal foil such as an aluminum foil, or It may be a steel plate or the like.
Examples of the paper include imitation paper, fine paper, craft paper, art coated paper, caster coated paper, pure white roll paper, parchment paper, water resistant paper, glassine paper, and corrugated paper.
Examples of the metal foil include copper foil and aluminum foil.

  As a method of using the composition, it is sufficient to follow a conventional method. After applying to the base material, the active energy ray is irradiated, and the adhesive composition is made into a syrup, and then bonded to the other base material and heated. Methods and the like. The composition can be cured only by heating without irradiating active energy rays. However, when a thin film is used as a substrate, a large amount of polymerization heat is added to the laminate in addition to heat from heating. Therefore, the film is deformed and a good laminate cannot be obtained.

Coating on the substrate may be performed by a conventionally known method, natural coater, knife belt coater, floating knife, knife over roll, knife on blanket, spray, dip, kiss roll, squeeze roll, reverse roll, air blade , Curtain flow coater, comma coater, gravure coater, micro gravure coater, die coater and curtain coater.
Moreover, what is necessary is just to select the application | coating thickness of the composition of this invention according to the base material to be used and a use, However, Preferably it is 0.1-100 micrometers, More preferably, it is 1-25 micrometers.

Examples of the active energy rays include visible light, ultraviolet rays, X-rays, and electron beams, but ultraviolet rays are preferable because inexpensive devices can be used.
Various light sources can be used as the light source when cured by ultraviolet rays, and examples thereof include a pressurized or high pressure mercury lamp, a metal halide lamp, a xenon lamp, an electrodeless discharge lamp, a carbon arc lamp, and an LED.
In the case of curing with an electron beam, various devices can be used as the EB irradiation device that can be used, and examples thereof include a Cockloft-Waltsin type, a bandegraph type, and a resonance transformer type device.
Even when a plastic film or the like contains a pigment or the like and ultraviolet curing is difficult, the composition can be preferably cured by electron beam irradiation.

The composition of this invention expresses high adhesive force by laminating | stacking a film after irradiating an active energy ray, and heating a laminated body.
As heating temperature in this case, 30-120 degreeC is preferable, More preferably, it is 50-90 degreeC. By setting the heating temperature to 30 or more, the curing reaction can be efficiently carried out in a short time, and by setting the heating temperature to 120 ° C. or less, the plastic film can be prevented from thermal deformation.
Examples of the heating method include a hot air dryer.

8). Manufacturing method of laminated body The composition of this invention can be preferably used for manufacture of a laminated body.
As a preferable method for manufacturing a laminate, the following steps 1 to 3 are sequentially performed.
Step 1: The composition is applied to at least one of the substrates.
Process 2: Pasting another base material on the coated surface and irradiating active energy rays from either side of the base material, or irradiating active energy rays to the coated surface, then other base materials And paste.
Process 3: The laminated body obtained at the process 2 is heated.
In Step 1 to Step 3, the coating method, the active energy ray irradiation method and the heating method, and the conditions thereof may follow the same method as described above.

In this invention, after the said process 2 irradiates an active energy ray to the coating surface obtained at the process 1, it is a process of bonding with another base material, The coating surface after irradiating an active energy ray is used. The manufacturing method of the laminated body made into a semi-hardened state is preferable.
The manufacturing method of the said laminated body can be used suitably, when the base material to be used uses the material which does not permeate | transmit an active energy ray easily. For example, the case where the above-mentioned plastic film etc. contain a ultraviolet absorber or / and a pigment etc. is mentioned.

As a method for setting the coated surface in a semi-cured state, the irradiation intensity and irradiation time (conveyor speed) are adjusted as irradiation conditions for the active energy ray, and the integrated light amount that makes the composition semi-cured is appropriately set.
In the present invention, the semi-cured state means a state in which the cured film after irradiating the coated surface with active energy rays has tack with a tentacle. Furthermore, the state having tack in the present invention is a reaction calculated by measuring the infrared absorption spectrum of the composition before and after irradiation with active energy rays and calculating the absorption intensity change of the ethylenically unsaturated group in the composition before and after irradiation with active energy rays. It means that the rate is 5 to 60%.

  Laminates such as a laminate film obtained from the composition of the present invention are excellent in adhesive strength under high temperature and high humidity conditions. Therefore, optical films such as polarizing plates, protective films and retardation films used in liquid crystal display devices, etc. It can be suitably used for films that require durability, such as films and solar cell backsheets.

Examples of the method of use in the production of a polarizing plate include adhesion between a polarizer and a protective film, adhesion between a polarizer and a polarizer, and adhesion between a protective film and a retardation film. In this case, examples of the polarizer include polyvinyl alcohol and the like, examples of the protective film include triacetylacetylcellulose and polymethyl methacrylate, and examples of the retardation film include cycloolefin resins such as norbornene resin.
Examples of the method of use in the production of a polarizing plate include adhesion between a polarizer and a protective film, adhesion between a polarizer and a polarizer, and adhesion between a protective film and a retardation film. In this case, examples of the polarizer include polyvinyl alcohol and the like, examples of the protective film include triacetylacetylcellulose and polymethyl methacrylate, and examples of the retardation film include cycloolefin resins such as norbornene resin.
As a usage method in the production of a solar battery, it can be used for adhesion of a solar battery cell and a back sheet material. The solar battery cell corresponds to a non-film plastic, and a cell made of silicon or the like is sealed with an ethylene-vinyl acetate copolymer or the like. A back sheet material as a protective film is provided at the lower part of the cell, and can be used for bonding the lower part of the cell and the back sheet material.
Examples of the back sheet material include polyvinyl fluoride, PET film, cyclofin film, and polyolefin. Is used.
The backsheet material may be composed of a plurality of films, and can be used for bonding the respective films in the production of the backsheet material. Examples of the film in this case include PET film, cyclofin film, polyolefin, and aluminum foil.

  Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. In the following examples, “part” means wt%.

○ Examples 1 to 5 and Comparative Examples 1 to 4
The components (A) to (C), (F) and (G) shown in Table 1 and Table 2 below are dissolved by heating and stirring at 60 ° C. for 1 hour to remove the components (D) and (E). Obtained. About the mixture except the said (D) component and (E) component, the viscosity in 25 degreeC was measured with the E-type viscosity meter. The results are shown in Tables 1 and 2.
Immediately before use, the active energy ray-curable adhesive composition was produced by heating and stirring components (D) and (E) shown in Tables 1 and 2 below in the mixture at 30 ° C. for 1 hour.
The obtained composition was evaluated according to the following test method. The results are shown in Table 3.

The numbers in parentheses in Tables 1 and 2 mean the number of copies. The abbreviations in Tables 1 and 2 are as follows.
1) Component (A) KY-303: Polyether urethane acrylate, weight average molecular weight: 15,000, manufactured by Negami Kogyo Co., Ltd., trade name Art Resin KY-303
OT-1001: Polyester urethane acrylate, weight average molecular weight: 40,000, manufactured by Toagosei Co., Ltd., trade name Aronix OT-1001
UN-9200: Polycarbonate urethane acrylate, weight average molecular weight: 1,000, manufactured by Negami Kogyo Co., Ltd., trade name Art Resin UN-9200A
2) Component (B) HPA: 2-hydroxypropyl acrylate, Kyoeisha Chemical Co., Ltd. light ester HOP-A
-HBA: 4-hydroxybutyl acrylate, Osaka Organic Chemical Industry Co., Ltd. 4-HBA
3) Component (C) · IBXA: Isobornyl acrylate, manufactured by Kyoeisha Chemical Co., Ltd. Light acrylate IB-XA
# 190: Ethyl carbitol acrylate, Osaka Organic Chemical Industry Co., Ltd. Viscoat 190
THFA: Tetrahydrofurfuryl acrylate, Kyoeisha Chemical Co., Ltd. light acrylate THF-A
DMAA: dimethylacrylamide, manufactured by Kojin Co., Ltd. DMAA
M-140: N-acryloyloxyethyl hexahydrophthalimide, manufactured by Toagosei Co., Ltd. Aronix M-140
FA-513AS: dicyclopentanyl acrylate, manufactured by Hitachi Chemical Co., Ltd. FA-513AS
4) Component (D) TPA-100: polyisocyanate of hexamethylene diisocyanate, Duranate TPA-100 manufactured by Asahi Kasei Chemicals Corporation
CNL-45: Polyisocyanate made from a reaction product of tolylene diisocyanate and trimethylolpropane, Nippon Polyurethane Co., Ltd. Coronate L-45
5) Component (E) PV: t-hexyl peroxypivalate, manufactured by NOF Corporation Perhexyl PV
-BP: Niper BO, manufactured by NOF Corporation Benzoyl peroxide
6) Component (F) TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, DAROCUR TPO manufactured by BASF
Irg819: Bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, manufactured by BASF IRGACURE819
Irg184: 1-hydroxy-cyclohexyl-phenyl-ketone, IRSFACURE184 manufactured by BASF
7) Component (G) AO-80: 3,9-bis [2- {3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5.5] undecane, Adeka Corporation Adeka Stub AO-80
TV900: Benzotriazole ultraviolet absorber, TINUVIN900 manufactured by BASF

-Manufacturing method of a laminated body The laminated body was manufactured using the following 4 types of plastic films.
PET: PET film, Toray Industries, Inc. Lumirror T-60 (50 μm)
COP: cycloolefin film, ZEONOR (100 μm) manufactured by Nippon Zeon Co., Ltd.
OPP: Biaxially stretched polypropylene film, Santox Co., Ltd. Santox-OP PA-21 (40 μm)
EVA: Ethylene vinyl acetate resin-based sheet, Hasegawa Chemical Industries, Ltd. San-A sheet (1 mm)
After applying the composition obtained above on a plastic film to a thickness of 25 μm with a bar coater, it is cured by ultraviolet irradiation at a conveyor speed of 30 m / min using a 120 W / cm condensing metal halide lamp. In a semi-cured state. The ultraviolet intensity was 500 mW / cm ² and the integrated light intensity was 170 mJ / cm ² (both values at 365 nm). When the cured film after UV irradiation was touched, it had tack.
In order to confirm the semi-cured state of the compositions of Examples and Comparative Examples, infrared absorption spectra of the compositions before and after irradiation with active energy rays were measured using a Spectrum 100 FTIR Spectrometer (manufactured by Perkin-Elmer). The reaction rate was calculated from the change in absorption intensity of the acryloyl group before and after irradiation with active energy rays. The results are shown in Table 3.

  Next, another plastic film was bonded to produce a laminate film as a test body.

Using the obtained test body, it heated at the temperature of 60 degreeC and 80 degreeC for 24 hours, respectively, and manufactured the laminated body.
Thereafter, the peel strength was measured with a tensile tester (Instron 5564 manufactured by Instron Japan Company Limited) under the following conditions.
As a heating method, a hot air dryer was set to a temperature of 60 ° C. and 80 ° C., respectively, and a test specimen was placed therein and heated for 24 hours.
-Test piece: 25 mm x 100 mm
Test method: T-shaped peeling / peeling speed: 200 mm / min
Next, the test body after heating at three temperatures in the same manner as described above was subjected to a high temperature test and a hot water test under the following conditions, and then peel strength was measured under the same method and conditions as described above. Those without numerical values are those in which the laminate was peeled off in warm water.
-After a warm water immersion test: Table 4 shows the results of warm water at 85 ° C for 24 hours or more.

The compositions of Examples 1 to 5 which are the compositions of the present invention were excellent in initial adhesive strength and excellent in adhesive strength after hot water immersion.
In contrast, the compositions of Comparative Examples 1 and 2 that did not contain the component (B) and the component (D) did not give any adhesive strength even when bonded and heated after irradiation with active energy rays. Since the composition of Comparative Example 3 containing no component (A) has low curability by irradiation with active energy rays, unreacted components volatilized during heating, and an adhesive layer could not be obtained. Although the composition of Comparative Example 4 containing no component (E) can be semi-cured by irradiation with active energy rays, the reaction rate of the compound having an ethylenically unsaturated group cannot be increased during heating, so that the original adhesive strength is It was not obtained.

  The composition of the present invention can be used as an adhesive for various plastic films and the like, particularly as an adhesive for difficult-to-adhere plastics, and is particularly suitable for production of optical films such as liquid crystal display devices, solar battery backsheets and the like. Can be used.

Claims (12)

An active energy ray-curable adhesive composition for plastic films or sheets containing the following components (A) to (E) in the following proportions.
(A) Urethane (meth) acrylate, which is a compound obtained by reacting a polyol and an organic polyisocyanate reaction product with a hydroxyl group-containing (meth) acrylate: (A) to (C) components (hereinafter referred to as “curable components”) 10 to 70% by weight in the total amount of
(B) Compound having a hydroxyl group and one ethylenically unsaturated group in the molecule: 3 to 40% by weight in the total amount of the curable component
(C) Ethylenically unsaturated group-containing compound other than components (A) and (B): 27 to 65% by weight in the total amount of the curable component
(D) Polyisocyanate compound: 1 to 20% by weight based on the total amount of curable components
(E) Thermal polymerization initiator: 0.001 to 10% by weight based on the total amount of curable components The active energy ray-curable adhesive composition for plastic film or sheet according to claim 1 , further comprising (F) a radical photopolymerization initiator in an amount of 0.1 to 20% by weight based on the total amount of the curable component. . The component (A) is a reaction product of a diol having a polyether skeleton, a polyester skeleton or a polycarbonate skeleton, an organic diisocyanate, and a hydroxyl group-containing (meth) acrylate. 3. The plastic film or sheet according to claim 1 or claim 2 . An active energy ray-curable adhesive composition. The weight average molecular weight of (A) component is 3,000-40,000, The active energy ray hardening-type adhesive composition for plastic films or sheets of any one of Claims 1-3 . The component (B) is a compound having one hydroxyl group and one ethylenically unsaturated group, active energy ray curing for plastic film or sheet according to any one of claims 1 to 4. Mold adhesive composition. 6. The active energy ray-curable adhesive composition for plastic film or sheet according to claim 5 , wherein the component (B) is hydroxyalkyl (meth) acrylate. The component (C) is at least one selected from the group consisting of an acrylamide compound, a carbitol (meth) acrylate having an alkyl group having 1 to 12 carbon atoms, and a (meth) acrylate having an alicyclic skeleton. plastic films or sheets for radiation-curable adhesive composition according to any one of-claims 6. The active energy ray-curable adhesive composition for a plastic film or sheet according to any one of claims 1 to 7 , wherein the plastic film or sheet is a hardly adhesive plastic film or sheet. 9. The active energy ray-curable adhesive for plastic film or sheet according to claim 8 , wherein the plastic film or sheet is at least one selected from the group consisting of polyolefin, polyester, cycloolefin polymer and ethylene-vinyl acetate copolymer. Agent composition. The manufacturing method of the laminated body which implements the following process 1-process 3 sequentially.
Step 1: Apply the active energy ray-curable adhesive composition for plastic film or sheet according to any one of claims 1 to 9 to at least one of the substrates.
Process 2: Pasting another base material on the coated surface and irradiating active energy rays from either side of the base material, or irradiating active energy rays to the coated surface, then other base materials And paste.
Process 3: The laminated body obtained at the process 2 is heated. The step 2 is a step of irradiating the coated surface obtained in the step 1 with active energy rays and then pasting with another substrate, and the coated surface after irradiating the active energy rays is in a semi-cured state. The manufacturing method of the laminated body of Claim 10 . The manufacturing method of the laminated body of Claim 10 or Claim 11 whose heating temperature in the process 3 is 30-120 degreeC.