CN101790551A - Photocurable resin composition and method for producing the same - Google Patents

Abstract

Disclosed is a photocurable resin composition which is excellent in shapability before photocuring as well as solvent resistance and flexibility after photocuring. Also disclosed is a method for producing such a photocurable resin composition. Specifically disclosed is a photocurable resin composition containing a (meth)acryloyl-modified photocurable copolymer having a double-bond equivalent weight of 1.8-4.0 meq/g, which copolymer is obtained by reacting an epoxy group-containing copolymer having a (meth)acrylate monomer unit and an epoxy group-containing (meth)acrylate monomer unit with a (meth)acrylic acid. Also specifically disclosed is a method for producing a photocurable resin composition, which comprises a polymerization step wherein an epoxy group-containing copolymer is obtained by polymerizing a monomer for forming a (meth)acrylate monomer unit with a monomer for forming an epoxy group-containing (meth)acrylate monomer unit, and a following modification step wherein the epoxy group-containing copolymer is (meth)acryloyl-modified by reacting a (meth)acrylic acid with the epoxy group.

Description

Photocurable resin composition and manufacture method thereof

Technical field

The present invention relates to Photocurable resin composition and manufacture method thereof.More particularly, the present invention relates to the Photocurable resin composition and the manufacture method thereof of preceding embossability, the solvent resistance behind the photocuring and the flexible excellence behind the photocuring of photocuring.

Background technology

So far, light-cured resin has been used for various uses.For example, in the surface decoration material of the interior finish of buildings and bar and tame electrical article etc., light-cured resin be used on wood materials and mineral-type materials etc., the fitting release paper etc. of band embossing of formation, synthetic leather manufacturing usefulness of concavo-convex pattern of decoration sheet that the decoration sheet that is printed with wood grain style style etc. forms with member, embossing hologram etc.

As the decoration sheet member, usually, use the substrate sheets that contains thermoplastic resin to be provided with the member of light-cured resin layer widely.For forming this light-cured resin layer, use Photocurable resin composition.But this Photocurable resin composition is required embossing processing before photocuring, bending machining, and have processibility and operation and transportation property etc. that adhesion ground does not coil into web-like etc.In addition, behind the photocuring, in generations such as the part of having carried out embossing and bending machining do not ftracture, and excellent in scratching resistance and thermotolerance and solvent resistance etc. are essential.

In patent documentation 1, Photocurable resin composition is disclosed, it is as being used for the Photocurable resin composition of decoration sheet member, contains by to polymerization (methyl) acrylate with have polymkeric substance addition that the monomer of carboxyl forms and have the ester ring type compound of ethylenic unsaturated link(age) and epoxy group(ing) and the multipolymer of modification.

In addition, in the situation of the concavo-convex pattern that forms embossing hologram etc., for example, carry out following method: on base materials such as polyester film, apply Photocurable resin composition, form uncured Photocurable resin composition layer, afterwards, after giving various concavo-convex patterns to this Photocurable resin composition layer, make this resin combination layer photocuring, at concavo-convex pattern face evaporation metal that forms or the different layer of lamination specific refractory power, form diffraction grating, embossing hologram etc. afterwards.

In the patent documentation 2, Photocurable resin composition is disclosed, it is as the Photocurable resin composition of the concavo-convex pattern that forms embossing hologram etc., and containing urethane modified acroleic acid resinoid, releasing agent and urethane acrylate or polyester acrylate is neccessary composition.

In addition, in the release paper of the band embossing of synthetic leather manufacturing usefulness, on supporters such as paper, apply Photocurable resin composition, form uncured Photocurable resin composition layer, afterwards, extruding has the metal grain roller of concavo-convex style to this Photocurable resin composition layer, give the embossing style to this Photocurable resin composition layer after, expose by irradiation ultraviolet radiation, electron beam, make this Photocurable resin composition layer photocuring.Utilization is formed with the synthetic leather manufacturing usefulness of resin layer at this supporter the release paper of band embossing carries out the manufacturing of synthetic leather.

Photocurable resin composition is disclosed in patent documentation 3; it is as the resin combination of release paper of the band embossing that is used for synthetic leather manufacturing usefulness, contain isocyanate compound, have (methyl) acryl and can with film-forming resins such as the resultant of reaction (oligopolymer) of (methyl) acrylic compound of isocyanate compound reaction and methacrylic resin.

Patent documentation 1: the spy opens the 2003-136646 communique

Patent documentation 2: the spy opens the 2000-234041 communique

Patent documentation 3: the spy opens the 2005-186516 communique

Summary of the invention

The problem that invention will solve

Performance to the Photocurable resin composition requirement, every kind of purposes is various, in the situations such as release paper that are used for decoration sheet, embossing hologram and band embossing, before the photocuring of filming, non-adhesiveness and to utilize the processing suitability of embossing etc. and excellent light solidified etc. be necessary, in addition, behind photocuring, flexible (shock resistance, resistance to bending) and scratch resistance and solvent resistance etc. are necessary.

As the Photocurable resin composition that is used to satisfy these performances, for example, in the patent documentation 1, the resin that the ester ring type compound that use has an epoxy group(ing) and the multipolymer addition that is formed by (methyl) acrylate and ethylenic unsaturated carboxylic acid form, this resin contains and contain the many multipolymers of acid in manufacturing process, and therefore the solvent that can use is restricted, in addition, since high slightly as the ester ring type compound price with epoxy group(ing) of raw material, problems such as cost height therefore had.

In addition, in patent documentation 2, used the urethane modified acroleic acid resinoid that makes isocyanic ester and hydroxyl reaction and the mixture of urethane acrylate or polyester acrylate, but had problems such as cost of material height.

In addition, in patent documentation 3, the oligopolymer composition of bearing solidified nature and the mixture of bearing the resin of film-forming properties have been used, but owing to used opposite resinous principle, for having given play to mutual composition speciality, require the strictness control of Photocurable resin composition manufacture method, the fluctuation with manufacturing becomes problem such as big.

During performance that detailed description requires Photocurable resin composition, for example for decoration sheet, Photocurable resin composition before the photocuring, it is natural not having tackiness, when forming, gives the embossing style concavo-convex style, but, then require " embossability " in order to pursue darker, thin and good style.That is, the mould etc. that carries out having a concavo-convex style is to resin extruded etc., owing to complementally give the style that resin has with mould, for resin, " flexibility " that can give concavo-convex style is necessary, and on the other hand, it also is necessary keeping the hardness of shape.In addition, the resin combination behind the photocuring also requires excellent " solvent resistance ", " scratch resistance ", " thermotolerance " and " flexible " etc.

In the light-cured resin, have the opposite feature of " flexibility " and " hardness " concurrently, also have " solvent resistance " etc. and be not easy, must further improve " embossability " and " solvent resistance " etc.

The present invention finishes for solving above-mentioned problem in the past, so that Photocurable resin composition to be provided is purpose, when this Photocurable resin composition has film-forming properties, " non-adhesiveness " in the manufacturing before the essential photocuring, " embossability " and as goods " solvent resistance " and " scratch resistance " and " flexible " excellence behind the essential photocuring in various uses.

Be used to solve the means of problem

The present invention is as described below.

1. Photocurable resin composition; it is characterized in that; the light solidified multipolymer that to contain through (methyl) acryl modification and two key equivalent be 1.8～4.0meq/g, this light solidified multipolymer obtains by (methyl) vinylformic acid is reacted with the multipolymer that contains epoxy group(ing) (C) that comprises (methyl) acrylic ester monomer unit (A) and contain (methyl) acrylic ester monomer unit (B) of epoxy group(ing).

2. the Photocurable resin composition described in above-mentioned 1., the weight-average molecular weight of wherein above-mentioned light solidified multipolymer (Mw) is 8000～200000, and the second-order transition temperature of above-mentioned light solidified multipolymer (Tg) is 30～90 ℃.

3. the Photocurable resin composition described in above-mentioned 1. or 2., the hydroxyl value of wherein above-mentioned light solidified multipolymer are 100～230mg-KOH/g.

4. at least a in (methyl) isobornyl acrylate, (methyl) methyl acrylate, (methyl) butyl acrylate and (methyl) isobutyl acrylate of each described Photocurable resin composition in above-mentioned 1.～3., the monomer that wherein forms above-mentioned (methyl) acrylic ester monomer unit (A).

5. each described Photocurable resin composition in above-mentioned 1.～4., wherein forming the above-mentioned monomer that contains (methyl) acrylic ester monomer unit (B) of epoxy group(ing) is (methyl) glycidyl acrylate.

6. each described Photocurable resin composition in above-mentioned 1.～5., when wherein the above-mentioned weight % that contains the multipolymer (C) of epoxy group(ing) being counted 100 weight %, the above-mentioned content that contains (methyl) acrylic ester monomer unit (B) of epoxy group(ing) is 30～80 weight %.

7. the manufacture method of Photocurable resin composition; it is the manufacture method of each described Photocurable resin composition in above-mentioned 1.～6.; it is characterized in that having: make the monomer that forms above-mentioned (methyl) acrylic ester monomer unit (A) and form the monomer polymerization of above-mentioned (methyl) acrylic ester monomer unit (B) that contains epoxy group(ing) and obtain containing epoxy group(ing) multipolymer (C) polymerization process and make (methyl) vinylformic acid then and this epoxy reaction and the modified process that makes this multipolymer that contains epoxy group(ing) (C) carry out the modification of (methyl) acryl.

The effect of invention

Photocurable resin composition of the present invention; the light solidified multipolymer that to contain through (methyl) acryl modification and two key equivalent be 1.8～4.0meq/g; this light solidified multipolymer above-mentioned by making (methyl) vinylformic acid reacts with the above-mentioned multipolymer (C) that contains epoxy group(ing) that comprises above-mentioned (methyl) acrylic ester monomer unit (A) and above-mentioned (methyl) acrylic ester monomer unit (B) that contains epoxy group(ing) and obtains; therefore can form light solidified excellence, simultaneously embossability by having (methyl) acryl; solvent resistance behind the photocuring and scratch resistance and the flexible (resistance to bending behind the photocuring; shock resistance) You Yi Photocurable resin composition.

In addition, the weight-average molecular weight of above-mentioned light solidified multipolymer (Mw) is 8000～200000, and the second-order transition temperature of above-mentioned light solidified multipolymer (Tg) is under 30～90 ℃ the situation, can be formed on and be difficult to produce tackiness in the uncured resin, and the Photocurable resin composition of embossability excellence.

In addition, the hydroxyl value of light solidified multipolymer is under the situation of 100～230mg-KOH/g, can form the solvent resistance behind the photocuring and the Photocurable resin composition of flexible excellence.

In addition, the monomer that forms above-mentioned (methyl) acrylic ester monomer unit (A) is under at least a situation in (methyl) isobornyl acrylate, (methyl) methyl acrylate, (methyl) butyl acrylate and (methyl) isobutyl acrylate, can form and second-order transition temperature (Tg) can be set in optimum range, the Photocurable resin composition of embossability and flexible excellence.

In addition, the monomer that forms above-mentioned (methyl) acrylic ester monomer unit (B) that contains epoxy group(ing) is under the situation of (methyl) glycidyl acrylate, can be efficiently and introduce epoxy group(ing) at low cost reliably.

In addition, when the above-mentioned weight % that contains the multipolymer (C) of epoxy group(ing) is counted 100 weight %, the above-mentioned content that contains (methyl) acrylic ester monomer unit (B) of epoxy group(ing) is the situation of 30～80 weight %, can form the light solidified excellence, simultaneously the solvent resistance behind embossability and the photocuring and the Photocurable resin composition of flexible excellence.

In addition, according to the manufacture method of Photocurable resin composition of the present invention, can make the solvent resistance behind embossability, the photocuring and the Photocurable resin composition of scratch resistance and flexible excellence more efficiently, easily and reliably.

Embodiment

Below describe the present invention in detail.

[1] Photocurable resin composition

Photocurable resin composition of the present invention contains through the modification of (methyl) acryl and light solidified multipolymer that two key equivalents are 1.8～4.0meq/g, and this light solidified multipolymer obtains by (methyl) vinylformic acid is reacted with the multipolymer that contains epoxy group(ing) (C) that comprises (methyl) acrylic ester monomer unit (A) and contain (methyl) acrylic ester monomer unit (B) of epoxy group(ing).

Promptly; above-mentioned light solidified multipolymer obtains (methyl) vinylformic acid and the multipolymer that contains epoxy group(ing) (C) reaction that comprises (methyl) acrylic ester monomer unit (A) and contain (methyl) acrylic ester monomer unit (B) of epoxy group(ing), and quilt (methyl) acryl modification and two key equivalent are 1.8～4.0meq/g.

But, do not comprise above-mentioned (methyl) acrylic ester monomer unit (B) that contains epoxy group(ing) in above-mentioned (methyl) the acrylic ester monomer unit (A).

Should illustrate that, two key equivalents divide the meg of the double bond content among the sample 1g for the solid shape of this multipolymer in the multipolymer of (methyl) acryl modification, measure with the morpholine additive process herein.

So-called morpholine additive process is to have utilized the method for amine to the addition reaction of two keys.Particularly, carry out in the following order.

(1) sample is put into Erlenmeyer flask, accurately be weighed to 1mg.

(2) add acetone 10ml, sample dissolution.Next adds the aqueous acetic acid of 50 (v/v) % of 10ml morpholine solution [morpholine: methyl alcohol=1: 4 (v/v)], 1.5ml, after fully stirring, at room temperature leaves standstill 15 minutes.

(3) add 15ml acetonitrile and 10ml Glacial acetic acid again, fully stir.

(4) methanol hydrochloride solution with 0.5mol/L carries out titration.

(5) also carry out blank test simultaneously, calculate two key equivalents with following calculating formula.

Two key equivalents (meq/g)=f * (A-B)/(2S).

Wherein, A is the ml number of the 0.5mol/L methanol hydrochloride solution of sample titration needs, and B is the ml number of the 0.5mol/L methanol hydrochloride solution of blank test needs, and f is the titre (power value) of 0.5mol/L methanol hydrochloride solution, and S is the sample amount of taking (g).

In addition, in this manual, " (methyl) vinylformic acid " is used to comprise the implication of the one or both of vinylformic acid and methacrylic acid, and " (methyl) acrylate " is used to comprise the implication of the one or both of acrylate and methacrylic ester.

In addition, " (methyl) acryl " is used to comprise the implication of the one or both of acryl and methacryloyl.

Light solidified multipolymer among the present invention is for comprising (methyl) acrylic ester monomer unit (A) and containing the modification body of the multipolymer that contains epoxy group(ing) (C) of (methyl) acrylic ester monomer unit (B) of epoxy group(ing).

As " (methyl) acrylic ester monomer " that form above-mentioned (methyl) acrylic ester monomer unit (A), can enumerate (methyl) alkyl acrylate, ester ring type (methyl) acrylate, aromatic series (methyl) acrylate, acidiferous (methyl) acrylate, (methyl) vinylformic acid hydroxyalkyl acrylate, nitrogenous (methyl) acrylate, polyalkylene glycol (methyl) acrylate, polycaprolactone (methyl) acrylate, siliceous (methyl) acrylate, fluorine-containing (methyl) acrylate and various macromonomers etc.They can a kind separately or will be used in combination more than 2 kinds.

As above-mentioned (methyl) alkyl acrylate, can enumerate (methyl) methyl acrylate, (methyl) ethyl propenoate, (methyl) vinylformic acid n-propyl, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) 2-EHA, (methyl) Octyl acrylate, (methyl) lauryl acrylate and (methyl) stearyl acrylate ester etc.

As above-mentioned ester ring type (methyl) alkyl acrylate (mean and comprise the substituting group (be called " ester substituting group ") of ester ring type composition), can enumerate (methyl) vinylformic acid ring pentyl ester as the ester that constitutes acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid ring monooctyl ester, (methyl) vinylformic acid ring ester in the ninth of the ten Heavenly Stems, (methyl) isobornyl acrylate, (methyl) vinylformic acid norborneol ester, (methyl) vinylformic acid dicyclo amyl group ester, (methyl) vinylformic acid double cyclopentenyl ester, (methyl) vinylformic acid dicyclo amylene oxygen base alkyl ester and (methyl) vinylformic acid adamantane esters etc.

As above-mentioned aromatic series (methyl) acrylate, can enumerate (methyl) benzyl acrylate, (methyl) phenyl acrylate, (methyl) vinylformic acid 2-hydroxyl-3-phenoxy group propyl ester, (methyl) vinylformic acid phenoxy ethyl, to cumyl phenoxy group ethylene glycol (methyl) acrylate and phenoxy group polyoxyethylene glycol (methyl) acrylate etc.

As acidiferous (methyl) acrylate, can enumerate (methyl) alkyl acrylate that contains carboxylic acid residues and contain monomer of sulfonic acid moieties etc.

As above-mentioned (methyl) alkyl acrylate (mean and comprise carboxylic acid residues) that contains carboxylic acid residues, the various anhydride modified things of (methyl) propenoic acid beta-carboxyl ethyl ester, ω-carboxyl polyalkylene glycol (methyl) acrylate, ω-carboxyl polycaprolactone (methyl) acrylate and ω-hydroxyl (methyl) acrylate etc. are arranged as " ester substituting group ".Should illustrate, can replace containing (methyl) alkyl acrylate of carboxylic acid residues and use (methyl) vinylformic acid etc.

In addition, as the monomer that contains sulfonic acid moieties, can enumerate (methyl) vinylformic acid 2-sulfonic acid ethyl ester etc.

Under above-mentioned (methyl) acrylic ester monomer unit (A) comprises situation from the monomeric unit of acidiferous (methyl) acrylate, during from manufacturing and the stable aspect in when preservation is considered, when the whole weight of multipolymer (C) that will contain epoxy group(ing) is counted 100 weight %, the content that preferably makes this monomeric unit is below the 10 weight %, more preferably be below the 3 weight %, further preferably be below the 0.5 weight %.

As above-mentioned (methyl) vinylformic acid hydroxyalkyl acrylate, can enumerate (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, glycerine (methyl) acrylate, (methyl) vinylformic acid 3-chloro-2-hydroxy propyl ester, ω-hydroxyl polyalkylene glycol (methyl) acrylate and ω-hydroxyl polycaprolactone (methyl) acrylate etc.These (methyl) vinylformic acid hydroxyalkyl acrylates; preferably the hydroxyl value of (methyl) acryl modification body that will lump together with the hydroxyl that multipolymer (C) by containing epoxy group(ing) and (methyl) acrylic acid reaction generate is set at 100～230mg-KOH/g; more preferably 130～200mg-KOH/g, more preferably 150～190mg-KOH/g.Under the low situation of hydroxyl value, the resin behind the photocuring flexible impaired.The stability of the light solidified multipolymer under the too high situation in the infringement solvent is easy to generate separating out of resin etc. sometimes.

As above-mentioned nitrogenous (methyl) alkyl acrylate (mean and comprise nitrogen component), can enumerate (methyl) vinylformic acid dimethylamino ethyl ester, (methyl) vinylformic acid diethylamino ethyl ester, (methyl) alkyl acrylate phenylpiperidines ester and various (methyl) vinylformic acid imino alkyl ester (possessing ester group substituting group) etc. with imino-as " ester substituting group ".

In addition, except the macromonomer that constitutes by various (methyl) acrylic ester monomer shown in above-mentioned, can use silicone based (methyl) acrylate etc.

Should illustrate that above-mentioned various monomers can a kind use separately or will be used in combination more than 2 kinds.

In addition; as above-mentioned (methyl) acrylic ester monomer; for the second-order transition temperature (hereinafter to be referred as " Tg ") with the light solidified multipolymer after the modification of (methyl) described later acryl remains on optimum range (30～90 ℃), the Tg that preferably contains more than one its homopolymer is the monomer (hereinafter to be referred as " monomer of high Tg ") more than 100 ℃.As such example, various monomers such as methyl methacrylate, (methyl) isobornyl acrylate and (methyl) vinylformic acid dicyclo amyl group ester are arranged.In them, preferred (methyl) acrylic ester monomer that contains epoxy group(ing) (hereinafter to be referred as " monomer (b) ") copolymerization and the monomer of especially high Tg, the i.e. lower isobornyl methacrylate of price that contains (methyl) acrylic ester monomer unit (B) of epoxy group(ing) easily with formation described later.In addition, from hanging down aspect, also preferable methyl methyl acrylate with easy copolymerization of monomer (b) and price.

Only use the monomer of these high Tg, under the too high situation of Tg, use the lower monomer of Tg (Tg of homopolymer less than 100 ℃ monomer).Wherein, preferred high Tg monomer and with (methyl) butyl acrylate and (methyl) isobutyl acrylate of the copolymerization excellence of monomer (b).Wherein more preferably butyl methacrylate and Propenoic acid, 2-methyl, isobutyl ester.

As forming the above-mentioned monomer (b) that contains (methyl) acrylic ester monomer unit (B) of epoxy group(ing), can enumerate (methyl) glycidyl acrylate, (methyl) vinylformic acid methyl glycidyl ester, (methyl) vinylformic acid 3,4-epoxycyclohexyl methyl esters and (methyl) vinylformic acid ethylene imine ester etc.They can a kind use separately or will be used in combination more than 2 kinds.In them, to be big (methyl) glycidyl acrylate of epoxide equivalent can introduce excellence aspect the epoxy group(ing) to functional group's equivalent efficiently.In them, consider special preferable methyl glycidyl acrylate from obtaining easiness and hypotoxic viewpoint.

In addition, above-mentioned light solidified multipolymer can contain above-mentioned monomeric unit (A) and above-mentioned monomeric unit (B) other monomeric units in addition in the scope of not damaging the resin rerum natura.Other monomers as forming other monomeric units have styrene monomer, N-vinyl pyrrolidone, vinyl acetate, (methyl) vinyl cyanide etc.In them, especially preferably use as the monomeric vinylbenzene of high Tg, alpha-methyl styrene.But, these monomers damage and above-mentioned (methyl) acrylic ester monomer that contains as neccessary composition and the reactivity of monomer (b) sometimes, must be noted that polymerizing condition in the situation of use.

The above-mentioned multipolymer (C) of epoxy group(ing) that contains is for comprising above-mentioned (methyl) acrylic ester monomer unit (A) and the above-mentioned multipolymer that contains (methyl) acrylic ester monomer unit (B) of epoxy group(ing).Therefore, can use the multipolymer that (methyl) acrylic ester monomer and monomer (b) polymerization are obtained, perhaps with (methyl) acrylic ester monomer, monomer (b) and the multipolymer that can obtain with other monomer polymerizations of their copolymerization.Should illustrate that the multipolymer (C) that contains epoxy group(ing) has multipolymer as the epoxy group(ing) of reactive functional groups by comprising above-mentioned epoxy group(ing) (methyl) the acrylic ester monomer unit (B) that contains.

The above-mentioned weight % that contains the multipolymer (C) of epoxy group(ing) is counted under the situation of 100 weight %, contain the above-mentioned ratio that contains (methyl) acrylic ester monomer unit (B) of epoxy group(ing) that contains in the multipolymer (C) of epoxy group(ing) and be preferably 30～80 weight %, more preferably 40～70 weight %, more preferably 50～60 weight %.If less than 30 weight %; sometimes infringement comprises as solvent resistance and scratch resistance behind the photocuring of the composition of the light solidified multipolymer of (methyl) acryl modification body; surpass under the situation of 80 weight %; because the second-order transition temperature (Tg) of (methyl) acryl modification body (light solidified multipolymer) is low excessively; produce the tackiness of cured films, also damage embossability sometimes.

Above-mentioned light solidified multipolymer (below be also referred to as (methyl) acryl modification body) is to make (methyl) vinylformic acid and above-mentioned multipolymer (C) reaction that contains epoxy group(ing) and through the multipolymer of (methyl) acryl modification.

The above-mentioned multipolymer (C) that contains epoxy group(ing) has epoxy group(ing), by making (methyl) vinylformic acid and this epoxy reaction, epoxy group(ing) is carried out the modification of (methyl) acryl.Multipolymer through the modification of (methyl) acryl is the multipolymer with (methyl) acryl.

With respect to the epoxy group content of the multipolymer that contains epoxy group(ing) (C), preferably with the reaction of (methyl) vinylformic acid more than 80% equivalent, more preferably more than 90% equivalent.If the transformation amount, is not only damaged solvent resistance and scratch resistance and obdurability (flexible) behind the photocuring less than 80% equivalent, and, damage the security and the storage stability of goods sometimes because epoxy group(ing), (methyl) vinylformic acid are remaining.

In addition, in (methyl) vinylformic acid, preferred vinylformic acid.This is because compare with methacryloyl, can introduce the high acryl of light solidified.

That is, the light solidified multipolymer among the present invention is preferably the acryl modification body that vinylformic acid is obtained with multipolymer (C) reaction that contains epoxy group(ing).

Two key equivalents of above-mentioned (methyl) acryl modification body are 1.8～4.0meq/g, are preferably 2.3～3.6meq/g, more preferably 2.8～3.2meq/g.If two key equivalents of (methyl) acryl modification body are lower than 1.8meq/g, damage solvent resistance and scratch resistance behind the photocuring sometimes.In addition,,, produce the tackiness of cured films, also damage embossability sometimes because the second-order transition temperature (Tg) of (methyl) acryl modification body became low if two key equivalent is higher than 4.0meq/g.

The weight-average molecular weight (Mw) of the above-mentioned multipolymer (C) that contains epoxy group(ing) is preferred 8000～200000, and more preferably 30000～150000, more preferably 40000～100000.

In addition, the weight-average molecular weight (Mw) of (methyl) acryl modification body is preferred 8000～200000, and more preferably 15000～100000, more preferably 25000～80000.Containing the multipolymer (C) of epoxy group(ing) and the weight-average molecular weight (Mw) of (methyl) acryl modification body crosses when hanging down; in cured films, occur tackiness easily, also damage solvent resistance and scratch resistance and obdurability (flexible) behind embossing embossability and the photocuring sometimes.In addition, contain the weight-average molecular weight (Mw) of the multipolymer (C) of epoxy group(ing) and (methyl) acryl modification body when too high, resin viscosity rises, and handles becoming difficulty sometimes.

The weight-average molecular weight of weight-average molecular weight (Mw) for adopting GPC to measure under following condition determination should be described.

(1) post: " TSK-GEL MULTIPORE HXL-M * 4 " (Dong Caoshe manufacturing)

(2) column temperature: 40 ℃

(3) elutriant: tetrahydrofuran (THF) (THF)

(4) detector: RI

(5) detector temperature: 40 ℃

(6) reference material: polystyrene

Should illustrate that in this condition determination, containing the multipolymer (C) of epoxy group(ing) and (methyl) acryl modification body is that solvability in the tetrahydrofuran (THF) there are differences at elutriant, therefore can not merely compare molecular weight.

In addition, contain in the multipolymer (C) of epoxy group(ing), adopt the content of the composition (hereinafter referred to as " low molecular weight compositions ") of molecular weight below 5000 of above-mentioned GPC mensuration to be preferably below the 5 weight % of this multipolymer (C) total amount.When surpassing 5 weight %, occur tackiness easily in cured films, the batching property of sheet material is bad sometimes, the embossing embossability is impaired.

Therefore, preferably making the above-mentioned low molecular weight compositions that contains in the multipolymer (C) that contains epoxy group(ing) is 5 weight % form the monomer and the above-mentioned monomer (b) of above-mentioned (methyl) acrylic ester monomer unit (A) to get off polymerization.

Preferred 50～120 ℃ of the second-order transition temperature (Tg) of the above-mentioned multipolymer (C) that contains epoxy group(ing), more preferably 60～110 ℃, more preferably 70～100 ℃.

Should illustrate that the second-order transition temperature (Tg) of multipolymer (C) that contains epoxy group(ing) calculates according to following formula based on the monomer that is used for its formation.In addition, in this specification sheets, the second-order transition temperature (Tg) of calculating according to following formula is called design second-order transition temperature (design Tg) (following identical).

1/ design Tg=(w ₁/ Tg ₁+ w ₂/ Tg ₂+ w ₃/ Tg ₃+ ...+w _n/ Tg _n)

In following formula, 1,2,3...n (n is the integer more than 2) expression forms the monomeric kind of the multipolymer (C) that contains epoxy group(ing), Tg _nThe second-order transition temperature (Tg) of the monomeric homopolymer shown in the expression n, w _nThe weight ratio of monomeric unit in this multipolymer shown in the n during the expression multipolymer constitutes, design Tg represents to design second-order transition temperature (design Tg).

The second-order transition temperature of above-mentioned homopolymer (Tg) has adopted POLYMER HANDBOOK (JOHN WILLY﹠amp; SONS, INC) value of middle record.

In addition, preferred 30～90 ℃ of the second-order transition temperature (Tg) of above-mentioned (methyl) acryl modification body, more preferably 40～80 ℃, more preferably 50～70 ℃.If it is low excessively to contain the design second-order transition temperature (design Tg) and the second-order transition temperature (Tg) after the modification of (methyl) acryl of the multipolymer (C) of epoxy group(ing); in uncured film, produce tackiness; damage the batching property of sheet material sometimes; perhaps afterwards shape is defeated and dispersed because embossing sometimes is pressed into; so infringement embossing embossability also damages the scratch resistance of the resin behind the photocuring sometimes.If (Tg) is too high for second-order transition temperature, cured films becomes state really up to the mark, if so embossing do not apply extreme high temperature when being pressed into, just can not be pressed into deeply, in addition, also damage flexible (resistance to bending behind the photocuring) of the resin behind the photocuring sometimes.

Should illustrate that the second-order transition temperature (Tg) of above-mentioned (methyl) acryl modification body is according to JIS-K-7121, the intermediate glass transition temperature that adopts DSC (difference formula scanning calorimeter) to measure.

Preferred 100～the 230mg-KOH/g of hydroxyl value of (methyl) acryl modification body, more preferably 130～200mg-KOH/g, more preferably 150～190mg-KOH/g.Under the low situation of hydroxyl value, the resin behind the photocuring flexible impaired.Under the too high situation, stable impaired in the solvent, separating out etc. of resin taken place easily sometimes.

Should illustrate that so-called hydroxyl value is meant to be the method use ethanoyl agent of neutralization based on regulation, the milligram number of the calcium hydroxide that the acetic acid that generates when above-mentioned resin sample 1g is reacted is required.

In addition, Photocurable resin composition of the present invention can contain light trigger.

As this light trigger, can enumerate bisglyoxaline compounds, bitter almond oil camphor compounds, acetophenone compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear quinones, xanthone compounds, thioxanthone compounds, compound in triazine class and ketal compounds etc.As commercially available product, can enumerate the vapour Bart and plant Irgacure series, DAROCUR series, the KAYACURE series of Japanese chemical drug manufacturing and the SPEECURE series that LAMBSON society makes etc. that chemical is made.They can use separately or will be used in combination more than 2 kinds.

In addition, in Photocurable resin composition of the present invention, can contain stopper, tinting material, tensio-active agent and solvent etc. as required.

In addition, in Photocurable resin composition of the present invention, can contain other light solidified polymkeric substance.But in order to realize purpose of the present invention, the content of other light solidified polymkeric substance preferably is below the 50 weight % when Photocurable resin composition is all counted 100 weight %, more preferably is below the 30 weight %.

In addition, in the Photocurable resin composition of the present invention, can contain multifunctional (methyl) origoester acrylate equally.But, in order to obtain non-adhesiveness and the embossability before the photocuring, the content of multifunctional (methyl) origoester acrylate is all being counted Photocurable resin composition under the situation of 100 weight %, preferably be below the 30 weight %, more preferably be below the 10 weight %, more preferably be below the 3 weight %.

Above-mentioned multifunctional (methyl) origoester acrylate; in 1 molecule, has (methyl) acryl more than 2; as specific examples, can enumerate tristane dihydroxymethyl diacrylate; the ethylene oxide modification diacrylate of Bisphenol F; the ethylene oxide modification diacrylate of dihydroxyphenyl propane; the ethylene oxide modification diacrylate of isocyanuric acid; polypropyleneglycol diacrylate; polyethyleneglycol diacrylate; Viscoat 295; the propylene oxide modification triacrylate of TriMethylolPropane(TMP); the ethylene oxide modification triacrylate of TriMethylolPropane(TMP); pentaerythritol triacrylate; tetramethylol methane tetraacrylate; two (TriMethylolPropane(TMP)) tetraacrylate; Dipentaerythritol five acrylate; dipentaerythritol acrylate; urethane acrylate etc.They can use separately or will be used in combination more than 2 kinds.

Alleged in this specification sheets " light solidified ", reaction when being meant irradiates light light such as () ultraviolet rays, electron beam, X ray, alpha-ray, β ray, gamma-rays, neutron ray isoradial isoreactivity energy line and solidified character.

Photocurable resin composition of the present invention is a resin combination of using up (light such as ultraviolet ray), electron beam isoreactivity energy line curing, wherein, as active energy ray, preferably adopts ultraviolet ray or electron beam.

[2] purposes of Photocurable resin composition of the present invention

Photocurable resin composition of the present invention can be used for the formation of the release paper etc. of decoration sheet, the embossing hologram of building materials and internal and external ornament etc., the transfer foil with embossability and band embossing.

In the release paper of above-mentioned decoration sheet, band embossing, use under the situation of Photocurable resin composition of the present invention, close on upper stratas such as supporters and state Photocurable resin composition as the resin layer that comprises above-mentioned Photocurable resin composition.As this supporter, under the situation of decoration sheet, use the base material of metal species and mineral-type, under the situation of the release paper of being with embossing, use paper base material.Should illustrate that under the laminated situation that other resin layers are arranged, above-mentioned Photocurable resin composition can be laminated on other resin layers on the above-mentioned supporter.In addition, also resin layer such as laminated silicone resin on the resin layer of above-mentioned Photocurable resin composition can comprised.

[3] manufacture method of Photocurable resin composition

The manufacture method of Photocurable resin composition of the present invention; it is characterized in that having: make the monomer that forms above-mentioned (methyl) acrylic ester monomer unit (A) and form the monomer polymerization of above-mentioned (methyl) acrylic ester monomer unit (B) that contains epoxy group(ing) and obtain containing epoxy group(ing) multipolymer (C) polymerization process and make (methyl) vinylformic acid thereafter and this epoxy reaction and the modified process that makes this multipolymer that contains epoxy group(ing) (C) carry out the modification of (methyl) acryl.

By above-mentioned polymerization process and above-mentioned modified process, can obtain above-mentioned light solidified multipolymer.

In addition, in the present invention, also can have above-mentioned light solidified multipolymer and other composition blended mixed processes.

(1) polymerization process

The monomer that uses in the above-mentioned polymerization process comprises the monomer of above-mentioned formation (methyl) acrylic ester monomer unit (A) and forms the monomer of (methyl) acrylic ester monomer unit (B) that contains epoxy group(ing).In addition, as required, can use can with other monomers of these monomer copolymerizations.

In the polymerization process of the present invention, common being suitable for has the paradigmatic system of thermometer, whipping appts, dripping device, reactor, reflux cooling device, water distilling apparatus and nitrogen ingress pipe.

The preferred continuous monomeric above-mentioned polymerization process that carries out simultaneously of supplying with or supply with in batches.That is, preferably pass through the batch process of continuous processing or certain or variable interval with above-mentioned monomer supply response system.The feed speed of continuous processing situation can necessarily also can be indefinite.

Polymer solvent in the above-mentioned polymerization process can use any normally used organic solvent.For example, be ketones solvents such as pimelinketone, acetone, methyl ethyl ketone, methyl iso-butyl ketone (MIBK); Cellosolve kind solvents such as methylcyclohexane, methyl glycol acetate, ethyl cellosolve acetate, ethylene glycol butyl ether acetic ester; Esters solvents such as vinyl acetic monomer, N-BUTYL ACETATE, isoamyl acetate, gamma-butyrolactone etc.

The usage quantity of above-mentioned polymer solvent is different because of its kind, polymerizing condition etc., with respect to the above-mentioned monomer of 100 weight parts, is generally 50～1000 weight parts.

Above-mentioned polymerization process is suitable for the radical polymerization of having used polymerization starter usually.This polymerization starter can be selected according to polymerizing condition so long as decompose to generate the material of radical get final product under polymerizing condition.For example, can use hydrogen peroxide; Persulphates such as Sodium Persulfate, ammonium persulphate, Potassium Persulphate; Organo-peroxides such as hydroperoxide, dialkyl, peroxidation diacyl, peroxy esters, benzoyl peroxide, lauroyl peroxide; Peracetic acid, mistake succsinic acid; 2,2 '-Diisopropyl azodicarboxylate, 2,2 '-azo two (2, the 4-methyl pentane nitrile), 2,2 '-azo two azo-compounds such as (2-methylbutyronitriles) etc.They may be used alone or in combination of two or more kinds.

The usage quantity of above-mentioned polymerization starter is different because of its kind, polymerizing condition etc., with respect to the above-mentioned monomer of 100 weight parts, is generally 0.1～10 weight part.

Polymerization temperature is because of the differences such as kind of polymerization starter, and usually from 40～180 ℃, preferred 50～150 ℃, more preferably 60～130 ℃ scope is selected.

In addition, carry out polymerization under (normal pressure) or the pressurized conditions under atmospheric atmosphere, the amount of pressurization of pressurization situation comprises normal atmosphere, is generally 0.15～0.5MPa.

Polymerization time is different because of polymerization temperature and pressurized conditions etc., is 3～15 hours usually under atmospheric atmosphere.

(2) modified process

In this modified process, make the epoxy reaction of (methyl) vinylformic acid for the multipolymer that contains epoxy group(ing) (C) that obtains by above-mentioned polymerization process.

In the above-mentioned modified process, the multipolymer that contains epoxy group(ing) (C) solution after above-mentioned polymerization process finishes is used in the modification of (methyl) acryl, preferably with (methyl) vinylformic acid reaction more than 80% equivalent, and more preferably above (methyl) vinylformic acid of 90% equivalent.If less than 80% equivalent, owing to fully do not introduce two keys, not only damage solvent resistance and scratch resistance and obdurability (flexible) behind the photocuring sometimes, and because epoxy group(ing), (methyl) vinylformic acid are remaining, the security of goods, storage stability go wrong sometimes.

In addition, from comparing with methacryloyl, the more excellent consideration of the light solidified of acryl, in (methyl) vinylformic acid, preferred vinylformic acid.Use in acrylic acid situation, can introduce the high acryl of light solidified.

(methyl) acrylic acid addition preferably, adds the epoxy group(ing) with respect to the multipolymer that contains epoxy group(ing) (C), with the amount of (methyl) vinylformic acid reaction more than 80% equivalent.

The modification of above-mentioned (methyl) acryl preferably in solution, is carried out in the presence of tertiary amine catalyst, quaternary ammonium salt catalyst, tertiary phosphine catalyzer, quaternary alkylphosphonium salt catalyzer and organo-tin compound catalyzer etc.As specific examples, can enumerate tertiary amine catalysts such as dimethyl benzyl amine, triethylamine, quaternary ammonium salt catalyst such as Tetrabutyl amonium bromide, tetramethyl ammonium chloride, triphenyl phosphine, three fourth phosphines, 1, tertiary phosphine catalyzer such as two (diphenylphosphino) ethane of 2-, quaternary alkylphosphonium salt catalyzer such as tetraphenylphosphonibromide bromide, four butyl phosphonium bromides, organo-tin compound catalyzer such as dibutyl tin laurate.They may be used alone or in combination of two or more kinds.In them, be preferably tertiary phosphine.From " reacting (catalyst activity height) fast " and " being difficult to produce painted during heat-flash " aspect, preferred tertiary phosphine.In addition, in the tertiary phosphine, be preferably triphenyl phosphine.From " inexpensive and be easy to get " aspect, more preferably triphenyl phosphine.

In addition, the solvent of above-mentioned solution can use with above-mentioned polymerization process in the solvent phase that uses with solvent.

The temperature of reaction of above-mentioned (methyl) acryl modification and reaction times are according to the reaction solvent of selecting, pressure condition in the modified-reaction and different; pressure condition (is 0.2～0.3MPa) when comprising normal atmosphere under the pressurized conditions of 0.1～0.2MPa; usually temperature of reaction is 80～160 ℃, and the reaction times is 3～20 hours.

Under atmospheric atmosphere, temperature of reaction is 50～140 ℃ usually, and the reaction times is 5～50 hours.

Among the present invention, as mentioned above, can also have mixed processes.This mixed processes is with above-mentioned light solidified multipolymer and other composition blended mixed processes.As other compositions, can enumerate light trigger, stopper, antioxidant and tensio-active agent etc.

As above-mentioned light trigger, can enumerate bisglyoxaline compounds, bitter almond oil camphor compounds, acetophenone compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear quinones, xanthone compounds, thioxanthone compounds, compound in triazine class and ketal class etc.As commercially available product, can enumerate the vapour Bart and plant Irgacure series, DAROCUR series, the KAYACURE series of Japanese chemical drug manufacturing and the SPEECURE series that LAMBSON society makes etc. that chemical is made.

Embodiment

Specify the present invention by the following examples.

[1] manufacturing of Photocurable resin composition

(1) embodiment 1

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C1

In glass flask, put into the 90g methylethylketone as solvent with stirrer, dropping funnel, reflux cooler, nitrogen conduit and thermometer.,, prepare the monomer mixed solution formed by 10g isobornyl methacrylate, 40g methyl methacrylate and 50g glycidyl methacrylate herein as monomer, in flask input wherein 20%.With after the liquid heat to 80 in the flask ℃, with 2.5 hours monomer mixed solutions that drip all the other 80%, simultaneously, as polymerization starter, the solution that 2,2 of 1.0g '-azo two (2, the 4-methyl pentane nitrile) is dissolved in the 12g methylethylketone dripped with 3 hours.In addition, at 80 ℃ of following polyase 13s hour, obtain acrylic copolymer (multipolymer that the contains epoxy group(ing)) C1 that intramolecularly has epoxy group(ing) methyl ethyl ketone solution (Gu shape divides 50.1%, Mn=21000, Mw=63000, low molecular composition amount: 3.1%).

In addition, above-mentioned Mn is a number-average molecular weight, and above-mentioned Mw is weight-average molecular weight (as follows).

In addition, monomeric kind in this acrylic copolymer (multipolymer that contains epoxy group(ing)) C1 modulation and design Tg, Mn and the Mw in usage quantity and the acrylic copolymer are shown in Table 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D1

Will be with respect to the solution total amount that contains C1 that obtains in the aforesaid operations, added 0.05g hydroquinone monomethyl ether, 1.0g triphenyl phosphine, next 25g vinylformic acid, be arranged in the autoclave with the solution of the methylethylketone (25g) of vinylformic acid equivalent, under 0.15MPa pressurization (add up to 0.25MPa), 110 ℃ condition, make it to react 6 hours with normal atmosphere.The acid number of the solution that mensuration obtains, the result is 4mg-KOH/g (reactivity 97%), confirms that reaction finishes substantially.Obtain thus that solid shape divides 50.6%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D1 of Mn=18000, Mw=39000.

Should illustrate, carry out Gu the mensuration of shape branch concentration is as described below.

In the aluminium alms bowl, take the 3g sample and after smart the title, use automatically admittedly that shape is divided meter, dry under 195 ℃ of temperature, smart once again title the when becoming constant, calculate with dry before the ratio (as follows) of smart title value.

In addition, Tg, hydroxyl value, two key equivalent, Mn and the Mw with acryl modified condition and acryl modifier in the manufacturing of acryl modification body (light solidified multipolymer) D1 of embodiment 1 is shown in Table 2.

In addition, the abbreviation in the table is as described below.

IBX: isobornyl methacrylate

MMA: methyl methacrylate

IBMA: Propenoic acid, 2-methyl, isobutyl ester

NBMA: n-BMA

GMA: glycidyl methacrylate

In addition, " pressurization " in " pressure condition " in the table is to carry out 0.15MPa pressurization, adds up under the pressure condition of 0.25MPa with normal atmosphere and carried out the acryl modification.

[table 1]

[table 2]

(2) embodiment 2

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C2

Except using 40g isobornyl methacrylate and 60g glycidyl methacrylate as monomer, use 2 of 1.1g, 2 '-azo two (2, the 4-methyl pentane nitrile) as outside the polymerization starter, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C2 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.0%, Mn=19000, Mw=49000, low molecular composition amount: 3.2%).

In addition, design Tg, Mn and the Mw with monomeric kind and usage quantity and acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C2 of embodiment 2 is shown in Table 1 similarly to Example 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D2

Except solution total amount with respect to the C2 that obtains in the aforesaid operations; replacing 25g vinylformic acid and making acrylic acid usage quantity is outside the 30g, obtains similarly to Example 1 that solid shape divides 50.3%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D2 of Mn=13000, Mw=27000.

In addition, Tg, hydroxyl value, two key equivalent, Mn and the Mw with acryl modified condition and acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D2 of embodiment 2 is shown in Table 2 similarly to Example 1.

(3) embodiment 3

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C3

Except using 50g methyl methacrylate and 50g glycidyl methacrylate as the monomer, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C3 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.1%, Mn=21000, Mw=59000, low molecular composition amount: 2.9%).

In addition, design Tg, Mn and Mw in monomeric species and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C3 of embodiment 3 are shown in Table 1 similarly to Example 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D3

Except solution total amount, obtain similarly to Example 1 that solid shape divides 50.5%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D3 of Mn=17000, Mw=33000 with respect to the C3 that obtains in the aforesaid operations.

In addition, Tg, hydroxyl value, two key equivalent, Mn and Mw in acryl modified condition and the acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D3 of embodiment 3 are shown in Table 2 similarly to Example 1.

(4) embodiment 4

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C4

Except using 55g isobornyl methacrylate and 45g glycidyl methacrylate as monomer, use 2 of 1.1g, 2 '-azo two (2, the 4-methyl pentane nitrile) as outside the polymerization starter, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C4 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.2%, Mn=19000, Mw=50000, low molecular composition amount: 3.0%).

In addition, design Tg, Mn and Mw in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C4 of embodiment 4 are shown in Table 1 similarly to Example 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D4

Except solution total amount with respect to the C4 that obtains in the aforesaid operations; replacing 25g vinylformic acid and making acrylic acid usage quantity is outside the 22.5g, obtains similarly to Example 1 that solid shape divides 50.4%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D4 of Mn=20000, Mw=40000.

In addition, Tg, hydroxyl value, two key equivalent, Mn and Mw in acryl modified condition and the acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D4 of embodiment 4 are shown in Table 2 similarly to Example 1.

(5) embodiment 5

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C5

Except using 20g isobornyl methacrylate, 10g methyl methacrylate and 70g glycidyl methacrylate as monomer, use 2 of 1.1g, 2 '-azo two (2, the 4-methyl pentane nitrile) as outside the polymerization starter, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C5 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.0%, Mn=19000, Mw=50000, low molecular composition amount: 3.0%).

In addition, design Tg, Mn and Mw in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C5 of embodiment 5 are shown in Table 1 similarly to Example 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D5

Except solution total amount with respect to the C5 that obtains in the aforesaid operations; replacing 25g vinylformic acid and making acrylic acid usage quantity is outside the 35g, obtains similarly to Example 1 that solid shape divides 50.4%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D5 of Mn=12000, Mw=23000.

In addition, Tg, hydroxyl value, two key equivalent, Mn and Mw in acryl modified condition and the acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D5 of embodiment 5 are shown in Table 2 similarly to Example 1.

(6) embodiment 6

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C6

Except using 20g isobornyl methacrylate and 80g glycidyl methacrylate as monomer, use 2 of 1.2g, 2 '-azo two (2, the 4-methyl pentane nitrile) as outside the polymerization starter, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C6 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.4%, Mn=17000, Mw=44000, low molecular composition amount: 3.3%).

In addition, design Tg, Mn and Mw in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C6 of embodiment 6 are shown in Table 1 similarly to Example 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D6

Except solution total amount with respect to the C6 that obtains in the aforesaid operations; replacing 25g vinylformic acid and making acrylic acid usage quantity is outside the 40g, obtains similarly to Example 1 that solid shape divides 50.8%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D6 of Mn=11000, Mw=21000.

In addition, Tg, hydroxyl value, two key equivalent, Mn and Mw in acryl modified condition and the acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D6 of embodiment 6 are shown in Table 2 similarly to Example 1.

(7) embodiment 7

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C7

Except using 65g methyl methacrylate, 5g Propenoic acid, 2-methyl, isobutyl ester and 30g glycidyl methacrylate as monomer, use 2 of 1.2g, 2 '-azo two (2, the 4-methyl pentane nitrile) as outside the polymerization starter, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C7 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.2%, Mn=16000, Mw=42000, low molecular composition amount: 3.5%).

In addition, design Tg, Mn and Mw in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C7 of embodiment 7 are shown in Table 1 similarly to Example 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D7

Except solution total amount with respect to the C7 that obtains in the aforesaid operations; replacing 25g vinylformic acid and making acrylic acid usage quantity is outside the 15g, obtains similarly to Example 1 that solid shape divides 50.6%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D7 of Mn=14000, Mw=34000.

In addition, Tg, hydroxyl value, two key equivalent, Mn and Mw in acryl modified condition and the acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D7 of embodiment 7 are shown in Table 2 similarly to Example 1.

(8) embodiment 8

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C8

Has stirrer, dropping funnel, reflux cooler, in the glass flask of nitrogen conduit and thermometer, put into the 10g isobornyl methacrylate, 40g methyl methacrylate and 50g glycidyl methacrylate as monomer and 90g methylethylketone as solvent, after being heated to 80 ℃, with 3 hours to wherein dripping as 2 of the 1.0g of polymerization starter, 2 '-azo two (2, the 4-methyl pentane nitrile) is dissolved in solution in the 12g methylethylketone, in addition at 80 ℃ of following polyase 13s hour, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C8 that intramolecularly has epoxy group(ing) is (Gu shape divides 50.2%, Mn=16000, Mw=62000, low molecular composition amount: 5.8%).

In addition, design Tg, Mn and Mw in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C8 of embodiment 8 are shown in Table 1 similarly to Example 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D8

Except solution total amount, obtain similarly to Example 1 that solid shape divides 50.5%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D8 of Mn=17000, Mw=38000 with respect to the C8 that obtains in the aforesaid operations.

In addition, Tg, hydroxyl value, two key equivalent, Mn and the Mw with acryl modified condition and acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D8 of embodiment 8 is shown in Table 2 similarly to Example 1.

(9) embodiment 9

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C9

Obtain similarly to Example 1 acrylic copolymer (multipolymer that the contains epoxy group(ing)) C9 that intramolecularly has epoxy group(ing) methyl ethyl ketone solution (Gu shape divides 50.3%, Mn=21000, Mw=63000, low molecular composition amount: 3.1%).

In addition, design Tg, Mn and Mw in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C9 of embodiment 9 are shown in Table 1 similarly to Example 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D9

Except solution total amount with respect to the C9 that obtains in the aforesaid operations; depress under atmospheric atmosphere outside the reaction not adding, obtain similarly to Example 1 that solid shape divides 50.4%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D9 of Mn=18000, Mw=39000.

In addition, Tg, hydroxyl value, two key equivalent, Mn and the Mw with acryl modified condition and acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D9 of embodiment 9 is shown in Table 2 similarly to Example 1.

(10) embodiment 10

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C10

Except using 30g Propenoic acid, 2-methyl, isobutyl ester, 30g butyl methacrylate and 40g glycidyl methacrylate as the monomer, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C10 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.2%, Mn=20000, Mw=56000, low molecular composition amount: 3.1%).

In addition, design Tg, Mn and Mw in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C10 of embodiment 10 are shown in Table 1 similarly to Example 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D10

Except solution total amount with respect to the C10 that obtains in the aforesaid operations; replacing 25g vinylformic acid and making acrylic acid usage quantity is outside the 20g, obtains similarly to Example 1 that solid shape divides 50.5%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D10 of Mn=18000, Mw=40000.

In addition, acryl modified condition and the Tg in the acryl modification body, hydroxyl value, two key equivalent, Mn and Mw in the manufacturing of acryl modification body (light solidified multipolymer) D10 of embodiment 10 are shown in Table 2 similarly to Example 1.

(11) embodiment 11

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C11

Except using 65g isobornyl methacrylate and 35g glycidyl methacrylate as the monomer, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C11 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.1%, Mn=21000, Mw=59000, low molecular composition amount: 3.3%).

In addition, design Tg, Mn and Mw in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C11 of embodiment 11 are shown in Table 1 similarly to Example 1.

(b) modulation of acryl modification body (light solidified multipolymer) D11

Except solution total amount with respect to the C11 that obtains in the aforesaid operations; replacing 25g vinylformic acid and making acrylic acid usage quantity is outside the 17.5g, obtains similarly to Example 1 that solid shape divides 50.5%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D11 of Mn=18000, Mw=42000.

In addition, Tg, hydroxyl value, two key equivalent, Mn and Mw in acryl modified condition and the acryl modification body in acryl modification body (light solidified multipolymer) the D11 modulation of embodiment 11 are shown in Table 2 similarly to Example 1.

(12) embodiment 12

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C12

Except using 2 of 1.8g, 2 '-azo two (2, the 4-methyl pentane nitrile) as outside the polymerization starter, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C12 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.0%, Mn=14000, Mw=33000, low molecular composition amount: 4.8%).

In addition, design Tg, Mn and Mw in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C12 of embodiment 12 are shown in Table 1 similarly to Example 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D12

Except solution total amount, obtain similarly to Example 1 that solid shape divides 50.5%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D12 of Mn=11000, Mw=25000 with respect to the C12 that obtains in the aforesaid operations.

In addition, Tg, hydroxyl value, two key equivalent, Mn and Mw in acryl modified condition and the acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D12 of embodiment 12 are shown in Table 2 similarly to Example 1.

(13) embodiment 13

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C13

Except using 2,2 of 2.6g '-azo two (2, the 4-methyl pentane nitrile) as outside the polymerization starter, obtain intramolecularly similarly to Example 1 and have the methyl ethyl ketone solution of multipolymer C13 of epoxy group(ing) (Gu shape divides 49.9%, Mn=9000, Mw=20000, low molecular composition amount: 14.6%).

In addition, design Tg, Mn and Mw in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C13 of embodiment 13 are shown in Table 1 similarly to Example 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D13

Except solution total amount, obtain similarly to Example 1 that solid shape divides 50.2%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D13 of Mn=9000, Mw=18000 with respect to the C13 that obtains in the aforesaid operations.

In addition, Tg, hydroxyl value, two key equivalent, Mn and Mw in acryl modified condition and the acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D13 of embodiment 13 are shown in Table 2 similarly to Example 1.

(14) embodiment 14

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C14

Except using 2 of 5.0g, 2 '-azo two (2, the 4-methyl pentane nitrile) as outside the polymerization starter, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C14 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.0%, Mn=5000, Mw=9000, low molecular composition amount: 32.6%).

In addition, design Tg, Mn and Mw in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C14 of embodiment 14 are shown in Table 1 similarly to Example 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D14

Except solution total amount, obtain similarly to Example 1 that solid shape divides 50.3%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D12 of Mn=5000, Mw=9000 with respect to the C14 that obtains in the aforesaid operations.

In addition, Tg, hydroxyl value, two key equivalent, Mn and Mw in acryl modified condition and the acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D14 of embodiment 14 are shown in Table 2 similarly to Example 1.

(15) comparative example 1

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C15

Except using 30g isobornyl methacrylate, 60g methyl methacrylate and 10g glycidyl methacrylate as the monomer, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C15 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.1%, Mn=23000, Mw=61000, low molecular composition amount: 2.9%).

In addition, design Tg, Mn and Mw in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C15 of comparative example 1 are shown in Table 3.For the record method etc. in the table, identical with the situation of embodiment 1.

(b) manufacturing of acryl modification body (light solidified multipolymer) D15

Except solution total amount with respect to the C15 that obtains in the aforesaid operations; replacing 25g vinylformic acid and making acrylic acid usage quantity is outside the 5g, obtains similarly to Example 1 that solid shape divides 50.4%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D15 of Mn=23000, Mw=62000.

In addition, Tg, hydroxyl value, two key equivalent, Mn and Mw in acryl modified condition and the acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D15 of comparative example 1 are shown in Table 4.For the record method etc. in the table, identical with the situation of embodiment 1.

[table 3]

Table 3

[table 4]

Table 4

	Comparative example 1	Comparative example 2	Comparative example 3
				Light solidified multipolymer D	??D15	??D16	??D17
Add vinylformic acid amount [g]	??5	??12.5	??45
				Pressure condition	Pressurization	Pressurization	Pressurization
Temperature of reaction	??110℃	??110℃	??110℃

	Comparative example 1	Comparative example 2	Comparative example 3
				Reaction times	6 hours	6 hours	6 hours
Second-order transition temperature (Tg)	??107℃	??61℃	??27℃
				Hydroxyl value [mg-KOH/g]	??38	??88	??245
Two key equivalents [meq/g]	??0.7	??1.6	??4.4
				Number-average molecular weight Mn	??23000	??16000	??11000
Weight-average molecular weight Mw	??62000	??38000	??22000

(16) comparative example 2

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C16

Except using 50g methyl methacrylate, 25g Propenoic acid, 2-methyl, isobutyl ester and 25g glycidyl methacrylate as the monomer, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C16 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.3%, Mn=18000, Mw=54000, low molecular composition amount: 3.0%).

In addition, design Tg, Mn in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C16 of comparative example 2 and Mw and comparative example 1 similarly are shown in Table 3.

(b) manufacturing of acryl modification body (light solidified multipolymer) D16

Except solution total amount with respect to the D16 that obtains in the aforesaid operations; replacing 25g vinylformic acid and making acrylic acid usage quantity is outside the 12.5g, obtains similarly to Example 1 that solid shape divides 50.6%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D16 of Mn=16000, Mw=38000.

In addition, Tg, hydroxyl value, two key equivalent, Mn and Mw and comparative example 1 in acryl modified condition and the acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D16 of comparative example 2 similarly are shown in Table 4.

(17) comparative example 3

(a) modulation of acrylic copolymer (multipolymer that contains epoxy group(ing)) C17

Except using 10g isobornyl methacrylate and 90g glycidyl methacrylate as the monomer, the methyl ethyl ketone solution that obtains acrylic copolymer (multipolymer that the contains epoxy group(ing)) C17 that intramolecularly has epoxy group(ing) similarly to Example 1 is (Gu shape divides 50.1%, Mn=21000, Mw=59000, low molecular composition amount: 3.2%).

In addition, design Tg, Mn in monomeric kind and usage quantity and the acrylic copolymer in the modulation of acrylic copolymer (multipolymer that the contains epoxy group(ing)) C17 of comparative example 3 and Mw and comparative example 1 similarly are shown in Table 3.

(b) manufacturing of acryl modification body (light solidified multipolymer) D17

Except solution total amount with respect to the C17 that obtains in the aforesaid operations; replacing 25g vinylformic acid and making acrylic acid usage quantity is outside the 45g, obtains similarly to Example 1 that solid shape divides 50.2%, the methyl ethyl ketone solution (Photocurable resin composition) of acryl modification body (light solidified multipolymer) D17 of Mn=11000, Mw=22000.

In addition, Tg, hydroxyl value, two key equivalent, Mn and Mw and comparative example 1 in acryl modified condition and the acryl modification body in the manufacturing of acryl modification body (light solidified multipolymer) D17 of comparative example 3 similarly are shown in Table 4.

[2] performance evaluation of Photocurable resin composition

Use the methyl ethyl ketone solution of the acryl modification body that obtains in embodiment 1～14 and the comparative example 1～3, light modulated curable resin composition as described below.Use these Photocurable resin compositions, make the test film and the cured film test film of cured films, carry out following performance evaluation (a)～(f).Its evaluation result is shown in table 5 and the table 6.

(1) making of the test film of cured films

The Irgacure907 (the vapour Bart plants the chemical manufacturing) that adds 1.0 weight % in the methyl ethyl ketone solution of acryl modification body is as light trigger, the light modulated curable resin composition.Use the excellent spreader of coiling that said composition be coated with on sheet glass or PET film so that thickness is 20 μ m, 120 ℃ of dryings 1 minute down, obtain the test film of cured films with throughcirculation dryer.

(2) making of the test film of cured film

To under air atmosphere, shine 500mJ/cm by the test film of the above-mentioned cured films that obtains ²Ultraviolet ray, obtain the test film of cured film.

Estimate for following project.

(a) " tackiness " of cured films estimated

Will by the test film of the above-mentioned cured films that obtains (supporter: sheet glass) be heated to all temps after, estimate film coated surface and refer to touch tackiness.Judge based on following benchmark.

◎: imperceptible basically tackiness in 80 ℃ the test.

Feel tackiness in zero: 80 ℃ the test.

△: feel tackiness in 60 ℃ the test.

△ ^*: feel tackiness in 50 ℃ the test.

*: feel adhesion in 40 ℃ the test.

(b) " compression distance " of cured films estimated

With micro-hardness tester when changing temperature and being pressed into pressure condition to by the test film of the above-mentioned cured films that obtains (supporter: sheet glass) carry out indentation test, " compression distance " of the degree of depth that is pressed into when estimating expression and being pressed into certain pressure.Judge based on following benchmark.

◎: compression distance is darker relatively.

Zero: compression distance is shallow relatively slightly.

△: compression distance is relatively very shallow.

*: almost can not be pressed into.

(c) cured films " being pressed into retentivity " estimated

Use micro-hardness tester when changing temperature and being pressed into pressure condition to test film (supporter: sheet glass) be pressed into by the above-mentioned cured films that obtains, after being pressed into certain pressure, compression distance remains to " being pressed into retentivity " of which kind of degree when estimating the expression relief pressure respectively.Judge based on following benchmark.

Should illustrate, take into account " compression distance " and " being pressed into retentivity " both the time, " embossability " is good.

◎: compression distance is roughly kept intact.

Zero: compression distance keeps good relatively.

△: compression distance is difficult to keep relatively.

△ ^*: compression distance relatively more is hard to keep.

*: the compression distance antipode is hard to keep.

Should illustrate, take into account " compression distance " of (b) and (c) " being pressed into retentivity " both the time, can be described as " embossability " good resin.

(d) cured film is flexible

Change degree makes the above-mentioned cured film that obtains with hand test film (supporter: the bending PET film), the cracking of evaluation overlay film in the not damaged scope of PET film.Judge based on following benchmark.

Zero: even bends does not produce cracking yet in filming

△: during bends, produce cracking in filming

*: during slight bending, produce cracking in filming

(e) solvent resistance of cured film

Will be by the test film (supporter: methyl iso-butyl ketone (MIBK) on overlay film surface point sheet glass) of the above-mentioned cured film that obtains, at room temperature place after 12 hours and wipe, afterwards, carry out scraping experiment with nail, comparison point has the part of solvent and the easy degree of scratch of the part of solvent is not arranged.Judge based on following benchmark.

◎: the easy degree indifference of scratch.

Zero: point has the part scratch a little easily of solvent.

△: point has the part of solvent to be easy to produce scratch.

△ ^*: point has the part of solvent obviously to be easy to generate scratch.

*: powerful wiping time point has the part of solvent to peel off.

* *: point has the part of solvent to peel off easily.

Should illustrate, will be evaluated as between " △ evaluation " and " * evaluation ", and the conduct " △ that in performance evaluation, can allow according to purposes ^*Estimate ".

(f) scratch resistance of cured film

(supporter: scraping experiment is carried out with nail in overlay film surface sheet glass), the easy degree of the scratch between comparative sample to the test film by the above-mentioned cured film that obtains.Judge based on following benchmark.

◎: almost do not have scratch.

Zero: be difficult to scratch relatively.

△: relatively easily injured.

*: produce peeling off of film during powerful the scraping.

[table 5]

[table 6]

Table 6

[3] effect of embodiment

By the result of table 5 and table 6 as can be known; two key equivalents after the modification of (methyl) acryl are at the embodiment 1～14 of the preferable range of 1.8～4.0meq/g, and are all excellent for all assessment items of " tackiness of cured films ", " compression distance ", " being pressed into retentivity ", " cured film flexible ", " solvent resistance of cured film " and " scratch resistance of cured film ".

By comparison, " compression distance " of comparative example 1 (two key equivalents are 0.7meq/g) and " cured film flexible " and " solvent resistance of cured film " are poor as can be known.In addition, comparative example 3 (two key equivalents are 4.4meq/g) produces " tackiness of cured films " at low temperatures, in addition, can not keep the degree of depth that is pressed into.

Form the embodiment 1～14 of the GMA of the acrylic ester monomer unit (B) that contains epoxy group(ing) as can be known, for the evaluation of physical property excellence of above-mentioned resin in the preferable range of 30～80 weight %.

By comparison, " compression distance " of comparative example 1 (GMA is 10 weight %), " cured film flexible ", " solvent resistance of cured film " and " scratch resistance of cured film " are poor as can be known.In addition, comparative example 3 (GMA is 90 weight %) produces " tackiness of cured films ", in addition, can not keep the degree of depth that is pressed into.

The embodiment 1～13 of weight-average molecular weight Mw in 10000～200000 scopes of (methyl) acryl modification body is all excellent for all assessment items of " tackiness of cured films ", " compression distance ", " being pressed into retentivity ", " cured film flexible ", " solvent resistance of cured film " and " scratch resistance of cured film " in addition, as can be known.

By comparison, " being pressed into retentivity " of embodiment 14 " the weight-average molecular weight Mw of (methyl) acryl modification body is 9000 " is slightly impaired as can be known.

In addition, embodiment 1～9 and the embodiment 12～14 of the second-order transition temperature of (methyl) acryl modification body in 30～90 ℃ of scopes as can be known, the evaluation of physical property of above-mentioned resin is more excellent.

In contrast, embodiment 10 (Tg is 28 ℃) produces " tackiness of cured films " a little at low temperature, and the maintenance of " being pressed into retentivity " is slightly impaired.In addition, embodiment 11 (Tg is 91 ℃) " compression distance ", " solvent resistance of cured film " and " scratch resistance of cured film " are also slightly impaired.

In addition, hydroxyl value is at the embodiment 1～14 of the preferable range of 100～230mg-KOH/g as can be known, and is all excellent for all assessment items of " tackiness of cured films ", " compression distance ", " being pressed into retentivity ", " cured film flexible ", " solvent resistance of cured film " and " scratch resistance of cured film ".

By comparison, " compression distance " of comparative example 1 (hydroxyl value is 38mg-KOH/g), " cured film flexible ", " solvent resistance of cured film " and " scratch resistance of cured film " are poor as can be known.In addition, comparative example 3 (hydroxyl value is 245mg-KOH/g) produces " tackiness of cured films " at low temperatures, in addition, can not keep compression distance.

Utilize possibility on the industry

Photocurable resin composition of the present invention, can be used for building materials and internal and external ornament etc. decoration sheet, embossing hologram, have the transfer foil of embossability and with the formation of processing release paper of embossing etc.

Claims (7)

1. Photocurable resin composition; it is characterized in that; the light solidified multipolymer that to contain through (methyl) acryl modification and two key equivalent be 1.8～4.0meq/g, this light solidified multipolymer obtains by (methyl) vinylformic acid is reacted with the multipolymer that contains epoxy group(ing) (C) that comprises (methyl) acrylic ester monomer unit (A) and contain (methyl) acrylic ester monomer unit (B) of epoxy group(ing).

2. the described Photocurable resin composition of claim 1, the weight-average molecular weight of wherein above-mentioned light solidified multipolymer (Mw) is 8000～200000, and the second-order transition temperature of above-mentioned light solidified multipolymer (Tg) is 30～90 ℃.

3. claim 1 or 2 described Photocurable resin compositions, the hydroxyl value of wherein above-mentioned light solidified multipolymer is 100～230mg-KOH/g.

4. at least a in (methyl) isobornyl acrylate, (methyl) methyl acrylate, (methyl) butyl acrylate and (methyl) isobutyl acrylate of each described Photocurable resin composition in the claim 1～3, the monomer that wherein forms above-mentioned (methyl) acrylic ester monomer unit (A).

5. each described Photocurable resin composition in the claim 1～4, wherein forming the above-mentioned monomer that contains (methyl) acrylic ester monomer unit (B) of epoxy group(ing) is (methyl) glycidyl acrylate.

6. each described Photocurable resin composition in the claim 1～5, when wherein the above-mentioned weight % that contains the multipolymer (C) of epoxy group(ing) being counted 100 weight %, the above-mentioned content that contains (methyl) acrylic ester monomer unit (B) of epoxy group(ing) is 30～80 weight %.

7. the manufacture method of Photocurable resin composition; it is the manufacture method of each described Photocurable resin composition in the claim 1～6; it is characterized in that having: make the monomer that forms above-mentioned (methyl) acrylic ester monomer unit (A) and form the monomer polymerization of above-mentioned (methyl) acrylic ester monomer unit (B) that contains epoxy group(ing) and obtain containing epoxy group(ing) multipolymer (C) polymerization process and make (methyl) vinylformic acid thereafter and this epoxy reaction and the modified process that makes this multipolymer that contains epoxy group(ing) (C) carry out the modification of (methyl) acryl.