CN104169331A

CN104169331A - Photocurable resin composition, image display device, and method for producing image display device

Info

Publication number: CN104169331A
Application number: CN201380013596.2A
Authority: CN
Inventors: 冈崎哲也; 木村阳一; 刘顺林; 和田真幸; 滨田启司; 铃木荣司
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Showa Denko Materials Co ltd
Priority date: 2012-03-12
Filing date: 2013-03-06
Publication date: 2014-11-26
Also published as: WO2013137087A1; JPWO2013137087A1; TW201406799A; KR20140133563A

Abstract

A photocurable resin composition comprising (A) a compound having a structural unit derived from polybutadiene, (B) a compound represented by general formula (1), (C) a thiol compound having a group represented by general formula (II) and (D) a photopolymerization initiator, wherein (A1) a compound having a (meth)acryloyl group and also having a structural unit derived from polybutadiene is contained as the component (A). The photocurable resin composition has excellent curability, a proper viscosity and good compatibility and can be used as one of constituent materials for an image display device. (In general formula (1), R1 represents a hydrogen atom or a methyl group; R2 represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms; and n represents a numeral value of 1 to 7.) (In general formula (II), R3 and R4 independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms; q represents an integer of 0 to 3; and * represents a bonding site).

Description

Photocurable resin composition, image show the manufacture method with device and image demonstration device

Technical field

The present invention relates to image show mitigation with anti-cracking, stress and the impact of device useful and Photocurable resin composition that the transparency is excellent, used the image of this resin combination to show to show the manufacture method of using device with device and this image.

Background technology

As the representational image demonstration device that has carried image display panel, can exemplify liquid-crystal display device.Liquid-crystal display has the liquid-crystal display panel of the blooming such as two lip-deep polaroids that comprises liquid crystal cells and be pasted on this liquid crystal cells etc. with device.This liquid crystal cells be by the thickness that is formed with from the teeth outwards transparency electrode, pattern of pixels etc. be about 1mm left and right 2 glass substrates across the gap configuration of several microns of left and right, in this gap filling liquid crystal being sealed to form.

Above-mentioned liquid-crystal display is very thin with panel, easily produce cut; therefore particularly in mobile phone, game machine, digital camera, vehicle-mounted purposes etc., conventionally use and there is the liquid-crystal display device that is provided with the structure of transparent front panel (protection panel) at the front surface of above-mentioned liquid-crystal display panel across certain space.

In addition show with starting to be equipped with touch panel in device with images such as watch-dogs at mobile phone, game machine, digital camera, on-vehicle parts, notebook computer, desktop computer, computer in recent years.This image that is equipped with touch panel shows the stepped construction that is formed as protecting panel, touch panel, image-display units with device, is protecting between panel and image-display units, is protecting between panel and touch panel and have air between touch panel and image-display units.

The existence of the air in these spaces can become the reason of scattering of light, and becomes the reduction of contrast gradient, brightness and transmittance and the major cause of the reduction of the image quality brought due to ghost image.

In order to prevent this drawback, propose to replace air in above-mentioned space segment and buried (for example, referring to patent documentation 1～4) with weighting materials such as resins.But, about in patent documentation 1～4, propose bury weighting material at space segment, there is following such problem.

,, for the oil using in patent documentation 1, for the sealing difficulty of Leakage prevention, and likely invade in the material that liquid crystal panel uses.Also have in addition oil leakage in the time that front panel ftractures the problem such as to go out.

The unsaturated polyester using in patent documentation 2 is easily coloured to yellow, is not preferably applied to liquid-crystal display device.

There is following problem in the silicone using in patent documentation 3: closing force is little, needs other tackiness agent for fixing, and therefore technique becomes numerous and diverse, and due to also not too large with the bonding force of tackiness agent, therefore applies while impact, can peel off and enter bubble.

The bonding force of the polymkeric substance of the Acrylic Acid Monomer using in patent documentation 4 is little, if bantam does not need tackiness agent in addition, but for the front panel that supports large-scale liquid-crystal display device needs tackiness agent in addition, it is numerous and diverse that technique becomes.Also can produce in addition because raw material only forms by monomer that therefore viscosity is low, cure shrinkage large thereby is difficult to make equably the problem of large-area film.

In addition; as showing for example, resin combination with the above-mentioned space of device (protect between panel and image-display units, protect the space between panel and touch panel and between touch panel and image-display units) for burying image; in the time using hot curing resin composition, be subject to showing as image the restriction of the heat resisting temperature of the component parts of using device.

Therefore,, as showing with the resin combination in the above-mentioned space of device for burying image, inquired into use Photocurable resin composition.

Prior art document

Patent documentation

Patent documentation 1: Japanese kokai publication hei 05-011239 communique

Patent documentation 2: Japanese kokai publication hei 03-204616 communique

Patent documentation 3: Japanese kokai publication hei 06-059253 communique

Patent documentation 4: TOHKEMY 2004-125868 communique

Summary of the invention

The problem that invention will solve

But; show with in device at image; in order to improve the contrast gradient etc. that shows image, conventionally carry out arranging with the width of regulation along the neighboring of protection panel the light shielding part (for example, having illustrated in Fig. 1 and 2 that the image that possesses the protection panel 40 that is provided with light shielding part 41 shows liquid-crystal display device 1A, the 1B with one of device) of frame shape.This light shielding part has the function of the unwanted photoresistance of image display panel periphery being broken, prevented the reduction of the demonstration grade causing because of light leak.

But; for the image demonstration device that is provided with light shielding part on protection panel; in the time Photocurable resin composition being filled in above-mentioned space; (be equivalent to the part of the P of Fig. 1 and 2 for the such shadow part of the posterior components that is filled into this light shielding part; below also referred to as " shadow part ") space in Photocurable resin composition; do not have sufficient light to arrive, produce and hinder curing problem.

For example in framework, be assembled with protection panel be set on the image-display units of liquid-crystal display panel, fill Photocurable resin composition betwixt, while carrying out rayed from protection panel side; (be equivalent to the part of the Q of Fig. 1 and 2 than the framework (light shielding part) of protection panel part more in the inner part; below also referred to as " transmittance section ") light can see through, but be filled in framework (light shielding part) thus the Photocurable resin composition of posterior components likely do not irradiated fully to solidify by light and can not carry out fully.

If tree oil/fat composition curing insufficient, can greatly damage image and show the quality with device, becomes the major reason that reliability reduces.

The object of the present invention is to provide and only there is solidifying the excellent solidified nature (below also referred to as " solidified nature at light shielding part place ") of carrying out fully and thering is the good Photocurable resin composition of suitable viscosity, consistency, used the image of this resin combination to show to show the manufacture method with device with device and this image on the such shadow part of the posterior components by can make light shielding part to the exposure of transmittance section.

For solving the means of problem

People of the present invention find that the Photocurable resin composition that contains special component can solve above-mentioned problem, thereby have completed the present invention.

The invention provides following (1)～(7).

(1) Photocurable resin composition, it contains:

(A) there is the compound of the structural unit that comes from polyhutadiene;

(B) compound shown in following general formula (1);

(C) there is the mercaptan compound of the group shown in following general formula (II); And

(D) Photoepolymerizationinitiater initiater,

Wherein, as (A) composition, contain the compound that (A1) has (methyl) acryl and have the structural unit that comes from polyhutadiene.

(in general formula (1), R ¹represent hydrogen atom or methyl, R ²represent the alkyl that hydrogen atom or carbon number are 1～12, n represents 1～7 number.)

(the R in general formula (II) ³and R ⁴represent independently that respectively hydrogen atom or carbon number are 1～5 alkyl, q represents 0～3 integer.* represent bonding part.)

(2), according to the Photocurable resin composition above-mentioned (1) Suo Shu, wherein, (C) composition is the mercaptan compound shown in following general formula (2).

(the R in general formula (2) ³and R ⁴represent independently that respectively hydrogen atom or carbon number are 1～5 alkyl, p represents 1～6 integer, and q represents 0～3 integer, and A represents the organic group of p valency.)

(3) according to the Photocurable resin composition above-mentioned (1) or (2) Suo Shu, wherein, the R in described general formula (1) ²that carbon number is 4～12 alkyl.

(4) according to the Photocurable resin composition described in any one in above-mentioned (1)～(3), it does not contain in fact organic solvent, and the viscosity of described Photocurable resin composition at 25 DEG C is 500～5000mPas.

(5) according to the Photocurable resin composition described in any one in above-mentioned (1)～(4), wherein, (C) content of composition is with respect to (A)～(C) total amount of composition is 3～30 quality %.

(6) according to the Photocurable resin composition described in any one in above-mentioned (1)～(5), wherein, content (A1) is 25～100 quality % with respect to the total amount of (A) composition.

(7) according to the Photocurable resin composition described in any one in above-mentioned (1)～(6); wherein; as (A) composition, further contain the compound that (A2) do not have (methyl) acryl and have the structural unit that comes from polyhutadiene.

(8), according to the Photocurable resin composition above-mentioned (7) Suo Shu, wherein, (A1) composition and (A2) mass ratio of composition ((A1)/(A2)) are 25/75～95/5.

(9) according to the Photocurable resin composition described in any one in above-mentioned (2)～(8), wherein, the A in described general formula (2) be following formula (C-1) or (C-2) shown in group or the carbon number alkylidene group that is 1～12.

(formula (C-1) or (C-2) in, * represents bonding part, X ¹～X ⁷representing independently respectively singly-bound or can having substituent carbon number is 1～12 alkylidene group.)

(10) according to the Photocurable resin composition described in any one in above-mentioned (1)～(9), wherein, (B) content of composition is with respect to (A)～(C) total amount of composition is 1～40 quality %.

(11) according to the Photocurable resin composition described in any one in above-mentioned (1)～(10), wherein, (A) content of composition is with respect to (A)～(C) total amount of composition is 50～98 quality %.

(12) an image demonstration device, it is the image demonstration device with stepped construction, described stepped construction comprises:

There is the image-display units of image displaying part;

There is the protection panel of light shielding part along neighboring; And

Be present in the resin layer between described image-display units and described protection panel,

Wherein, described resin layer is the cured article of the Photocurable resin composition described in any one in above-mentioned (1)～(11).

(13) an image demonstration device, it is the image demonstration device with stepped construction, described stepped construction comprises:

There is the image-display units of image displaying part;

Touch panel;

There is the protection panel of light shielding part along neighboring; And

Be present in the resin layer between described touch panel and described protection panel,

(14) a kind of image shows the manufacture method with device; it is that the protection panel that has image-display units or the touch panel of image displaying part and have light shielding part along neighboring is configured in opposite directions, made Photocurable resin composition in their gap and makes the curing image of described Photocurable resin composition show the manufacture method with device

Wherein, make in above-mentioned (1)～(11) Photocurable resin composition described in any one in described gap, and at least carry out rayed from described protection panel side described Photocurable resin composition is solidified.

The effect of invention

The solidified nature excellence at the light shielding part place of Photocurable resin composition of the present invention, there is suitable viscosity, consistency is good.In addition, the transparency of the cured article of Photocurable resin composition and specific refractory power excellence, there is suitable specific inductivity.

In addition; according to the manufacture method of graphical representation device of the present invention; owing to using the Photocurable resin composition of solidified nature excellence at light shielding part place; therefore in the time having used the protection panel that possesses light shielding part along neighboring; even carry out rayed from this protection panel side; the posterior components of light shielding part also can be solidified fully, can the productivity graphical representation device of quality bills of materials excellence well.

Brief description of the drawings

Fig. 1 is the sectional view that schematically represents to show as image of the present invention an embodiment of the liquid-crystal display device of an example using device.

Fig. 2 schematically represents to show the sectional view with the liquid-crystal display use device that is equipped with touch panel of an embodiment of the liquid-crystal display device of an example of device as image of the present invention.

Embodiment

Below by embodiment to Photocurable resin composition of the present invention, used the image of this resin combination to show to be described in detail with the manufacture method of device and image demonstration device.It should be noted that, this embodiment does not limit the present invention.

" (methyl) acrylate " in this specification sheets refers to " acrylate " and " methacrylic ester " corresponding with it.Similarly, " (methyl) vinylformic acid " refers to " vinylformic acid " and " methacrylic acid " corresponding with it, and " (methyl) acryl " refers to " acryl " and " methacryloyl " corresponding with it.

[Photocurable resin composition]

Photocurable resin composition of the present invention (being also only called below " resin combination ") contains compound, (C) shown in compound, (B) general formula (1) that (A) have the structural unit that comes from polyhutadiene and has the mercaptan compound of the group shown in general formula (II) and (D) Photoepolymerizationinitiater initiater; wherein; as (A) composition, contain the compound that (A1) has (methyl) acryl and have the structural unit that comes from polyhutadiene.In addition, not damaging in the scope of effect of the present invention, can also contain other additive except above-mentioned (A)～(D) composition.Below each composition is described.

< (A) composition: the compound > with the structural unit that comes from polyhutadiene

Resin combination of the present invention contains the compound with the structural unit that comes from polyhutadiene as (A) composition.

(A) composition is divided into (A1) and has (methyl) acryl and have the compound (below also referred to as " polyhutadiene (methyl) acrylate ") of the structural unit that comes from polyhutadiene and (A2) do not have (methyl) acryl and have the compound of the structural unit that comes from polyhutadiene, and resin combination of the present invention contains as the polyhutadiene of (A1) composition (methyl) acrylate.

From improving the viewpoint of solidified nature of light shielding part of gained resin combination, (A1) content of composition with respect to the total amount of (A) composition be preferably 25 quality % above, more preferably 30 quality % above, more preferably 40 quality % above, be further preferably 52 quality % more than.

((A1) composition: there is (methyl) acryl and there is the compound of the structural unit that comes from polyhutadiene)

As the thering is (methyl) acryl and there is the compound of the structural unit that comes from polyhutadiene of (A1) composition, for example, can enumerate compound that makes polybutadiene diol and have the monoisocyanates compound of (methyl) acryl to react and to obtain etc.

In above-mentioned polyhutadiene, there is the polyhutadiene with " Isosorbide-5-Nitrae-structural unit " or " 1,2-structural unit ".Here, " Isosorbide-5-Nitrae-structural unit " in polyhutadiene refer to following chemical formula (1t) or (1c) shown in such structural unit, " 1,2-structural unit " refers to such repeating unit shown in following chemical formula (1d).

As the polybutadiene diol mainly with Isosorbide-5-Nitrae-structural unit, for example, can enumerate Poly bd R-45HT, Poly bd R-15HT (Isosorbide-5-Nitrae-structural unit containing proportional: 80%, bright dipping Xing Chan company system, trade(brand)name).

As mainly having 1, the polybutadiene diol of 2-structural unit, can exemplify the compound shown in following general formula (1a), can enumerate particularly G-1000 (1,2-structural unit containing proportional: 85%), G-2000 (1,2-structural unit containing proportional: 85%), G-3000 (1,2-structural unit containing proportional: 90%) (being trade(brand)name above, Tso Tat Co., Ltd., Japan's system).

(in formula (1a), n1 represents 1～60 integer.)

As in (A1) composition 1,2-structural unit and 1,4-structural unit containing proportional (1,2-structural unit/1,4-structural unit), be preferably 10/90～98/2, more preferably 60/40～98/2, more preferably 70/30～97/3, be further preferably 80/20～95/5.

As the above-mentioned monoisocyanates compound with (methyl) acryl, can enumerate (methyl) vinylformic acid 2-isocyanato ethyl ester, (methyl) vinylformic acid 2-isocyanato propyl ester, (methyl) vinylformic acid 3-isocyanato propyl ester etc.

In addition, polybutadiene diol can be carried out with for example the reacting of monoisocyanates compound with (methyl) acryl under the existence of the catalyzer such as stopper and dibutyltin dilaurate such as p methoxy phenol.

In the present invention, (A1) weight-average molecular weight of composition (Mw), from the viewpoint of solidified nature, flexible and operability, is preferably 1,000～30,000, more preferably 2,000～20,000, more preferably 3,000～10,000.

It should be noted that, in this specification sheets, the weight-average molecular weight (Mw) of (A) composition is to utilize the value that gel permeation chromatography (GPC) is measured, the typical curve of use polystyrene standard converts and obtain.In addition, when number-average molecular weight, weight-average molecular weight and the dispersity molecule that molecular weight is Mi in (A) composition exists Ni as given a definition.

(a) number-average molecular weight (Mn)

Mn＝Σ(N _iM _i)/ΣNi＝ΣX _iM _i

(X _i=molecular weight is M _ithe mole fraction=N of molecule _i/ Σ N _i)

(b) weight-average molecular weight (Mw)

Mw＝Σ(N _iM _i ²)/ΣN _iM _i＝ΣW _iM _i

(W _i=molecular weight is M _ithe weight fraction=N of molecule _im _i/ Σ N _im _i)

(c) molecular weight distribution (dispersity)

Dispersity=Mw/Mn

(A1) content of composition is from the viewpoint of the raising of the solidified nature of light shielding part, with respect to the total amount of (A) composition be preferably 25～100 quality %, more preferably 30～100 mass parts, more preferably 40～100 quality %, be further preferably 45～100 quality %.

((A2) composition: do not there is (methyl) acryl and there is the compound of the structural unit that comes from polyhutadiene)

In resin combination of the present invention; can only contain (A1) composition as (A) composition; but from the viewpoint of solidified nature, cure shrinkage and operability and obtain the viewpoint of the resin combination with proper viscosity; as (A) composition, preferably side by side contain with (A1) composition the compound (below also referred to as " (A2) composition ") that (A2) do not have (methyl) acryl and have the structural unit that comes from polyhutadiene.

As the compound of (A2) composition, for example, can enumerate polybutadiene diol, polyhutadiene dicarboxylic acid, maleation polyhutadiene, dienite, can react with the multipolymer of butadiene copolymer, polybutadiene diol and the compound with isocyanate group the compound, the polybutadiene diol that obtain and react the compound, the polyhutadiene dicarboxylic acid that obtain react acquisition compound, polyhutadiene dicarboxylic acid with the compound with hydroxyl with the compound with carboxyl and react with the compound with epoxy group(ing) the compound etc. of acquisition.

As the polyhutadiene dicarboxylic acid mainly with 1,2-structural unit, for example, can enumerate C-1000 (1,2-structural unit containing proportional: more than 85%, Tso Tat Co., Ltd., Japan's system, trade(brand)name).

As mainly having 1, the dienite of 2-structural unit, can enumerate B-1000 (1,2-structural unit containing proportional: 85%), B-2000 (1,2-structural unit containing proportional: 85%), B-3000 (1, containing of 2-structural unit is proportional: 90%) (being trade(brand)name above, Tso Tat Co., Ltd., Japan's system).

React the compound obtaining as above-mentioned polybutadiene diol with the compound with isocyanate group, for example, can enumerate TEA-1000, TE-2000 (Tso Tat Co., Ltd., Japan's system, trade(brand)name).

React the compound obtaining as above-mentioned polyhutadiene dicarboxylic acid with the compound with epoxy group(ing), for example, can enumerate EPB13 (Tso Tat Co., Ltd., Japan's system, trade(brand)name).

(A1) composition and (A2) mass ratio of composition ((A1)/(A2)) from the viewpoint of the raising of the solidified nature of light shielding part and obtain the viewpoint of the resin combination with proper viscosity, are preferably 25/75～95/5, more preferably 30/70～90/10, more preferably 40/60～80/20, are further preferably 45/55～70/30.

If this mass ratio is more than 25/75, can improve the solidified nature at the light shielding part place of gained resin combination.And if this mass ratio is below 95/5, can make the resin combination with suitable viscosity.

The content of (A) composition in resin combination of the present invention with respect to (A) in resin combination～(C) total amount of composition be preferably 50～98 quality %, more preferably 60～94 quality %, more preferably 68～92 quality %, be further preferably 80～92 quality %.

If (A) content of composition is more than 50 quality %, can improves the solidified nature at the light shielding part place of gained resin combination, and can reduce specific inductivity.And if (A), the content of composition is below 98 quality %, owing to can guaranteeing (B) composition and (C) content of composition, therefore the resin combination with suitable viscosity can be made, and the transparency of the cured article of resin combination can be improved.

< (B) composition: the compound > shown in general formula (1)

Resin combination of the present invention contains the compound shown in following general formula (1) as (B) composition.

R in above-mentioned general formula (1) ¹represent hydrogen atom or methyl.

In addition, the R in above-mentioned general formula (1) ²represent the alkyl that hydrogen atom or carbon number are 1～12.The carbon number of this alkyl exceedes at 12 o'clock, and with the consistency variation of (A) composition, the transparency of cured article reduces, therefore not preferred.

Therefore, as R ²from making good with the consistency of (A) composition and making the good viewpoint of solidified nature of the light shielding part of gained resin combination, the alkyl that preferably carbon number is 4～12, the alkyl that more preferably carbon number is 5～11, the alkyl that further preferably carbon number is 6～10.

The alkyl that is 1～12 as carbon number, for example, can enumerate methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl etc.

In addition, abovementioned alkyl can be any of straight chain and attachment.

In addition, at least a portion of the hydrogen atom of these alkyl can be by replacements such as such as hydroxyl, halogen atom, alkyl, cycloalkyl, aryl, aralkyl, carbonyl, formyl radical, ester group, amide group, alkoxyl group, aryloxy, alkylthio, arylthio, amino, silyl, siloxyies.

N in above-mentioned general formula (1) represents 1～7 number, from (A) composition and (C) viewpoint of the consistency of composition, be preferably 1～6, more preferably 1～5, more preferably 3～5.

N exceedes at 7 o'clock, have with (A) composition and (C) consistency of composition reduce, the tendency of the transparent variation of cured article.In addition, the solidified nature at the light shielding part place of gained resin combination reduces, therefore not preferred.

In addition,, in the present invention, n refers to the mean value of the number of the ethylene oxide chain of the compound shown in general formula (1).

As the compound shown in above-mentioned general formula (1), for example, can enumerate (methyl) vinylformic acid phenoxy ethyl, butyl phenoxy polyoxyethylene glycol (methyl) acrylate, amyl group phenoxy group polyoxyethylene glycol (methyl) acrylate, hexyl phenoxy group polyoxyethylene glycol (methyl) acrylate, heptyl phenoxy group polyoxyethylene glycol (methyl) acrylate, Octylphenoxy polyoxyethylene glycol (methyl) acrylate, Nonylphenoxy polyoxyethylene glycol (methyl) acrylate, decyl phenoxy group polyoxyethylene glycol (methyl) acrylate etc.

These compounds can be used singly or in combination of two or more thereof.

In addition, as the preferred commercially available product of the compound shown in above-mentioned general formula (1), can enumerate FA-310A (Hitachi Chemical Co., Ltd.'s system, trade(brand)name, the R in formula (1) ¹for hydrogen atom, R ²for the mean value of hydrogen atom, the n compound that is 4), FA-314A (Hitachi Chemical Co., Ltd.'s system, trade(brand)name, the R in formula (1) ¹for hydrogen atom, R ²for the mean value of nonyl, the n compound that is 4).

As the weight-average molecular weight (Mw) of (B) composition, be preferably below 3000, more preferably 100～2800, more preferably 150～2000, be further preferably 200～1500.

The content of (B) composition in resin combination of the present invention is preferably 1～40 quality %, more preferably 3～30 quality %, 4～27 quality % more preferably with respect to (A) in resin combination～(C) total amount of composition.

If (B) content of composition is more than 1 quality %, can make the resin combination with suitable viscosity, the operability can make to be coated with time is good, and can reduce cure shrinkage.In addition, can make the solidified nature at light shielding part place of gained resin combination good, and can improve the transparency of cured article.

In addition, if (B) content of composition is below 40 quality %, can suppresses cure shrinkage and uprise.

< (B2) composition: the low molecular weight monomers > in the molecule except the compound shown in above-mentioned general formula (1) with 1 ethylenic unsaturated group

In addition, in resin combination of the present invention, can also contain the low molecular weight monomers (B2) in the molecule except the compound shown in above-mentioned general formula (1) with 1 ethylenic unsaturated group.

As such low molecular weight monomers (B2), for example, can enumerate compound having in (methyl) alkyl acrylate shown in following general formula (3) and molecule (methyl) acrylic and hydroxyl or ehter bond etc.

In above-mentioned general formula (3), R ¹¹represent hydrogen atom or methyl, R ¹²represent the alkyl that carbon number is 4～20.R ¹²from further giving the viewpoint of flexibility, the alkyl that preferably carbon number is 6～18, the alkyl that more preferably carbon number is 8～16.

As (methyl) alkyl acrylate shown in above-mentioned general formula (3), for example can enumerate (methyl) n-butyl acrylate, (methyl) tert-butyl acrylate, (methyl) isobutyl acrylate, (methyl) vinylformic acid n-pentyl ester, (methyl) vinylformic acid n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) 2-EHA, (methyl) isodecyl acrylate, the just own ester of (methyl) vinylformic acid, (methyl) stearyl acrylate ester, (methyl) lauryl acrylate, (methyl) tridecyl acrylate etc.These compounds can be used singly or in combination of two or more thereof.

As the compound in molecule with (methyl) acrylic and hydroxyl or ehter bond, for example, can enumerate (methyl) acrylate of the hydroxyls such as (methyl) vinylformic acid 2-hydroxy methacrylate, (methyl) vinylformic acid 1-hydroxy methacrylate, (methyl) vinylformic acid 2-hydroxy propyl ester, (methyl) vinylformic acid 3-hydroxy propyl ester, (methyl) vinylformic acid 1-hydroxy propyl ester, (methyl) vinylformic acid 4-hydroxyl butyl ester, (methyl) vinylformic acid 3-hydroxyl butyl ester, (methyl) vinylformic acid 2-hydroxyl butyl ester, (methyl) vinylformic acid 1-hydroxyl butyl ester; (methyl) acrylamide of the hydroxyls such as hydroxyethyl (methyl) acrylamide; The polyethyleneglycol such as Diethylene Glycol or triethylene glycol (methyl) acrylate; The polypropylene glycol such as dipropylene glycol or tripropylene glycol list (methyl) acrylate; Polytetramethylene glycol list (methyl) acrylate such as dibutylene glycol or three butyleneglycols; Acryloyl morpholines etc. are containing (methyl) acrylate of morpholinyl.

Wherein, the viewpoint of operability from wet-heat resisting reliability and while applying, preferably (methyl) acrylate of hydroxyl, containing (methyl) acrylate of morpholinyl, more preferably vinylformic acid 4-hydroxyl butyl ester, acryloyl morpholine.

These low molecular weight monomers (B2) can be used singly or in combination of two or more thereof.

As the weight-average molecular weight (Mw) of these low molecular weight monomers (B2), be preferably below 3000, more preferably 100～2800, more preferably 150～2000.

In addition, the content of low molecular weight monomers (B2) is preferably 0～30 mass parts, 0～15 mass parts more preferably with respect to (B) composition 100 mass parts.

< (C) composition: the mercaptan compound > with the group shown in general formula (II)

Resin combination of the present invention contains the mercaptan compound with the group shown in following general formula (II) as (C) composition.In addition, this compound can be used singly or in combination of two or more thereof.

R in above-mentioned general formula (II) ³and R ⁴represent independently that respectively hydrogen atom or carbon number are 1～5 alkyl, q represents 0～3 integer.* represent bonding part.

R ³and R ⁴represent independently that respectively hydrogen atom or carbon number are 1～5 alkyl, the alkyl that preferably hydrogen atom or carbon number are 1～3, more preferably hydrogen atom or methyl.In addition, abovementioned alkyl can be any of straight chain and attachment.

The alkyl that is 1～5 as carbon number, for example, can enumerate methyl, ethyl, propyl group, sec.-propyl, normal-butyl, sec-butyl, isobutyl-, the tertiary butyl, amyl group etc.

Q in general formula (II) represents 0～3 integer, preferably 1～2 integer, more preferably 1.

In addition, in the above-mentioned mercaptan compound with the group shown in general formula (II), from the viewpoint of the stability of gained resin combination, the mercaptan compound shown in preferred following general formula (2).

R in above-mentioned general formula (2) ³and R ⁴represent independently that respectively hydrogen atom or carbon number are 1～5 alkyl, the alkyl that preferably hydrogen atom or carbon number are 1～3, more preferably hydrogen atom or methyl.In addition, abovementioned alkyl can be any of straight chain and attachment.

P in general formula (2) represents 1～6 integer, preferably 1～4 integer, more preferably 2～4 integer.

Q in general formula (2) represents 0～3 integer, preferably 1～2 integer, more preferably 1.

In compound shown in above-mentioned general formula (2), from the viewpoint of the stability of gained resin combination, preferably q=1, R ³for methyl, R ⁴for the secondary mercaptan compound shown in the following general formula (2a) of hydrogen atom.

(in above-mentioned formula (2a), p represents 1～6 integer, and A represents the organic group of p valency.)

General formula (2) and (2a) in A represent the organic group of p valency, represent particularly the organic group of 1～6 valency.

As the organic group of 1 valency, for example, can enumerate carbon number and be 1～12 alkyl, the cycloalkyl that carbon number is 3～12, the aryl that carbon number is 6～24, aralkyl, the carbonyl that carbon number is 6～24 and (refer to-CO-R.Wherein R is alkyl (alkyl that preferably carbon number is 1～6)), ester group (refer to-CO-O-R or-O-CO-R.Wherein R is alkyl (alkyl that preferably carbon number is 1～6)), formamyl etc.

The alkyl that is 1～12 as carbon number, can enumerate as the R in above-mentioned general formula (1) ²illustrated go out group.

The cycloalkyl that is 3～12 as carbon number, for example, can enumerate cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 1-adamantyl, 2-adamantyl, 1-norcamphyl, 2-norcamphyl etc.

The aryl that is 6～24 as carbon number, for example, can enumerate phenyl, xenyl, naphthyl etc.

The aralkyl that is 6～24 as carbon number, for example, can enumerate benzyl, styroyl, phenyl propyl etc.

As the organic group of divalent, for example, can enumerate carbon number and be arylidene that the carbon numbers such as 1～12 alkylidene group, cycloalkylidene that carbon number is 3～12, phenylene, biphenylene are 6～24, polyether-based, polysiloxane group, carbonyl, ester group, amide group, carbamate groups etc.

The alkylidene group that is 1～12 as carbon number, for example, can enumerate methylene radical, ethylidene, sub-n-propyl, isopropylidene, sub-normal-butyl, isobutylidene, pentylidene, hexylidene, sub-heptyl, octylene, 2-ethyl hexylidene, nonamethylene, sub-decyl, sub-undecyl, sub-dodecyl etc.

The cycloalkylidene that is 3～12 as carbon number, for example, can enumerate cyclopropylidene, sub-cyclobutyl, cyclopentylidene, cyclohexylidene, sub-ring octyl group, sub-ring decyl, 1,3-adamantyl etc.

As arylidene, for example, can enumerate 1,2-phenylene, 1, the phenylenes such as 3-phenylene, Isosorbide-5-Nitrae-phenylene, biphenylene, naphthylidene etc.

As polyether-based, for example, can enumerate polyethylene oxide base, poly(propylene oxide) base etc.

As polysiloxane group, for example, can enumerate polydimethylsiloxane, polydiethylsiloxane, polydiphenylsiloxane, PSI etc.

As the organic group of 3～6 valencys, for example, aliphatic alkyl that the carbon number that can enumerate 3～6 valencys with aliphatic chain is 1～12, there is ester ring type alkyl that the carbon number of 3～6 valencys of alicyclic structure is 3～12, there is the aromatic hydrocarbyl that the carbon number of 3～6 valencys of aromatic ring structure is 6～24 and there is heterocyclic radical containing 3～6 valencys of the heteroatomic heterocycle structures such as Sauerstoffatom, nitrogen-atoms, sulphur atom etc.

In addition, these organic groups A can further have substituting group.

The substituting group that can have as organic group A, for example, can enumerate hydroxyl, halogen atom, alkyl, cycloalkyl, aryl, aralkyl, carbonyl, formyl radical, ester group, amide group, alkoxyl group, aryloxy, alkylthio, arylthio, amino, silyl, siloxy-etc.

In the organic group of the p valency shown in these A, preferred following formula (C-1) or (C-2) shown in group or the carbon number alkylidene group that is 1～12.

Above-mentioned (C-1) or (C-2) in, * represents bonding part, X ¹～X ⁷representing independently respectively singly-bound or can having substituent carbon number is 1～12 alkylidene group.As this substituting group, can enumerate the identical group of substituting group that can have with above-mentioned organic group A.

As X ¹～X ⁷, the alkylidene group that preferably singly-bound or carbon number are 1～8, the alkylidene group that more preferably carbon number is 1～4, further preferred methylene radical or ethylidene.

The alkylidene group that is 1～12 as carbon number, the alkylidene group that preferably carbon number is 1～8, the alkylidene group that more preferably carbon number is 1～6, the alkylidene group that further preferably carbon number is 2～4.

As the particular compound of (C) composition, for example can enumerate 1, two (the 3-sulfydryl butyryl acyloxy) butane, 1,3 of 4-, 5-tri-(3-sulfydryl butyryl acyloxy ethyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone, tetramethylolmethane four (3-sulfydryl butyric ester) etc.

These compounds can use separately or two or more is used in combination.

In addition, these compounds can be used as Karenz MT series (" Karenz MT BD1 ", " Karenz MT NR1 ", " Karenz MT PE1 " etc.) and are obtained by Showa Denko K. K.

The content of (C) composition in resin combination of the present invention is from the solidified nature of the light shielding part of gained resin combination and the viewpoint of wet-heat resisting reliability, is preferably 1～30 quality %, more preferably 2～20 quality %, 3～12 quality % more preferably with respect to (A) in resin combination～(C) total amount of composition.

< (D) composition: Photoepolymerizationinitiater initiater >

As the Photoepolymerizationinitiater initiater using in the present invention (D), for example can enumerate benzophenone, N, N '-tetramethyl--4, 4 '-diaminobenzophenone (michaelis ketone), N, N-tetraethyl--4, 4 '-diaminobenzophenone, 4-methoxyl group-4 '-dimethylamino benzophenone, Alpha-hydroxy isobutyl-benzophenone, 2-ethyl-anthraquinone, tertiary butyl anthraquinone, 1, 4-dimethyl anthraquinone, 1-chloroanthraquinone, 2, 3-dichloroanthraquinone, 3-chloro-2-methyl anthraquinone, 1, 2-benzo anthraquinone, 2-phenyl anthraquinone, 1, 4-naphthoquinones, 9, 10-phenanthrenequione, thioxanthone, CTX, 1-hydroxycyclohexylphenylketone, 2, 2-dimethoxy-1, 2-diphenylethane-1-ketone, the aromatic ketone compounds such as 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, the bitter almond oil camphor compounds such as bitter almond oil camphor, methylbenzene acyloin, ethylbenzene acyloin, the benzoin ether compounds such as benzoin methylether, ethoxybenzoin, bitter almond oil camphor ethyl isobutyl ether, bitter almond oil camphor phenyl ether, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl] the Alpha-hydroxy alkyl phenones based compound such as-2-hydroxy-2-methyl-1-propane-1-ketone, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2,4,4-trimethylammonium-amyl group phosphine oxide, 2, the acylphosphine oxide based compounds such as 4,6-trimethylbenzoyl-diphenyl phosphine oxide, oligomeric (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone), β-(acridine-9-yl) acrylic acid ester cpds, 9-phenylacridine, 9-pyridyl acridine, 1, the acridine compounds such as 7-bis-acridines heptane, 2-(Chloro-O-Phenyl)-4, 5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4, 5-bis-(m-methoxyphenyl) imidazole dimer, 2-(adjacent fluorophenyl)-4, 5-diphenyl-imidazole dipolymer, 2-(o-methoxyphenyl)-4, 5-diphenyl-imidazole dipolymer, 2-(p-methoxyphenyl)-4, 5-diphenyl-imidazole dipolymer, 2, 4-bis-(p-methoxyphenyl) 5-phenylimidazole dipolymer, 2-(2, 4-Dimethoxyphenyl)-4, 5-diphenyl-imidazole dipolymer, 2-(to methyl mercapto phenyl)-4, 5-diphenyl-imidazole dipolymer etc. 2, 4, 5-triarylimidazoles dipolymer, benzil, 2,2-diethoxy acetophenone, benzil dimethyl ketal, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-morpholine-1-propane etc.

These light initiation polymerization agent (D) can use separately or two or more is used in combination.

Wherein, from suppressing the painted viewpoint to resin combination, preferably 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 1-[4-(2-hydroxyl-oxethyl)-phenyl] the Alpha-hydroxy alkyl phenones based compound such as-2-hydroxy-2-methyl-1-propane-1-ketone, two (2, 4, 6-trimethylbenzoyl)-phenyl phosphine oxide, two (2, 6-dimethoxy benzoyl)-2, 4, 4-trimethylammonium-amyl group phosphine oxide, 2, 4, the acylphosphine oxide based compounds such as 6-trimethylbenzoyl-diphenyl phosphine oxide, the material that oligomeric (2-hydroxy-2-methyl-1-(4-(1-methyl ethylene) phenyl) acetone) and they combine.

In addition; from obtaining the viewpoint of resin combination of making of the sheet material that is suitable for thick film; preferred two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2; 4; 4-trimethylammonium-amyl group phosphine oxide, 2,4, the acylphosphine oxide based compounds such as 6-trimethylbenzoyl-diphenyl phosphine oxide.

The content of (D) Photoepolymerizationinitiater initiater using in the present invention is from the viewpoint of solidified nature, with respect to (A)～(C) total amount 100 mass parts of composition be preferably 0.05～10 mass parts, more preferably 0.08～7 mass parts, more preferably 0.1～4 mass parts, be further preferably 0.2～2 mass parts.

Other additive > of <

Photocurable resin composition of the present invention can further coordinate other additive in the scope that does not hinder effect of the present invention.As other additive, for example, can enumerate stablizer, softening agent etc.

Stablizer improves the object of the stability of Photocurable resin composition and adds, for example, can enumerate triphenyl phosphite etc.

Softening agent regulates the object of the viscosity of Photocurable resin composition to add, and the polyester that for example can enumerate 2 yuan of acid and polyvalent alcohol is that softening agent, molecular chain are the polystyrene softening agent such as softening agent, polyurethane series softening agent, Poly-alpha-methylstyrene, polystyrene etc. by the liquid polyethers such as acrylic resin softening agent, polypropylene glycol or derivatives thereof of alkyl acrylate monomer units and/or alkyl methacrylate monomer cell formation.

In addition, Photocurable resin composition of the present invention is from wet-heat resisting reliability and suppress the viewpoint that the bubble cured article occurs, and does not preferably contain in fact organic solvent (solvent).

It should be noted that, " not containing in fact organic solvent " refer to and expressly do not add organic solvent, if do not make the significantly reduced degree of characteristic after the photocuring of Photocurable resin composition of the present invention, also can have micro-organic solvent.

Particularly, the content of organic solvent with respect to the total amount of resin combination be 1000ppm below, be preferably 500ppm following, more preferably 100ppm following, more preferably 10ppm following, further preferably do not contain organic solvent (0ppm) completely.

Here said " organic solvent " refer in molecule, do not there is ethylenic unsaturated group, at 25 DEG C for the boiling point under liquid and normal atmosphere is 250 DEG C of following organic compound.

(physical property of Photocurable resin composition)

The viscosity of Photocurable resin composition of the present invention at 25 DEG C is oozed out and the viewpoint of operability from suppressing, be preferably 500～5000mPas, more preferably 1,000～5,000mPas, more preferably 2,000～4,000mPas, be further preferably 2,500～3,800mPas.

In addition, the viscosity at 25 DEG C be use E type viscometer, 3 ° of cone rotors (cone rotor), with 0.5min ^-1the value recording, the value of the measuring method of recording based on embodiment specifically.

(physical property of the cured article of Photocurable resin composition)

The transmittance at the wavelength 440nm place when thickness 175nm of the cured article of Photocurable resin composition of the present invention is preferably more than 98%, more preferably more than 99%.

The specific refractory power of the cured article of Photocurable resin composition of the present invention is preferably 1.45～1.55, more preferably 1.47～1.53.

Specific inductivity when the frequency 1MHz of the cured article of Photocurable resin composition of the present invention is preferably 2.5～3.0, more preferably 2.7～2.9.If this specific inductivity is more than 2.5,, in the time that resin combination of the present invention is applied to touch panel purposes, the performance of replying of touch panel improves.And if this specific inductivity is below 3.0,, in the time being applied to touch panel purposes, can suppress the generation because replying too high caused flase operation.

In addition, these physics values are values of the measuring method recorded based on embodiment.

[image demonstration device]

Image demonstration of the present invention is the image demonstration device with stepped construction with device, and described stepped construction comprises: the image-display units with image displaying part; There is the protection panel of light shielding part along neighboring; And be present in the resin layer between described image-display units and described protection panel, wherein, described resin layer is the cured article of above-mentioned liquid Photocurable resin composition.

In addition, image demonstration of the present invention is the image demonstration device with stepped construction with device, and described stepped construction comprises: the image-display units with image displaying part; Touch panel; There is the protection panel of light shielding part along neighboring; And be present in the resin layer between described touch panel and described protection panel, wherein, described resin layer is the cured article of above-mentioned liquid Photocurable resin composition.

Below to describing with the liquid-crystal display device of an example of device as image demonstration.

Below to as describing with the liquid-crystal display device of an example of device by using the image of Photocurable resin composition manufacture of present embodiment to show.

< liquid-crystal display device >

Liquid-crystal display shown in Fig. 1 is stacked gradually the image-display units 1 that forms, is formed becoming the resin layer 32 of upper surface setting of polaroid 20 of visuognosis side of liquid-crystal display device and the protection panel 40 arranging in its surface by back light system 50, polaroid 22, liquid crystal display 10 and polaroid 20 with device 1A.Resin layer 32 is made up of the cured article of the Photocurable resin composition of present embodiment.In addition, protection panel 40 has light shielding part 41 along the neighboring of this protection panel.

In addition, Fig. 2 schematically represents to show the sectional view with the liquid-crystal display use device that is equipped with touch panel of an embodiment of the liquid-crystal display device of an example of device as image of the present invention.Liquid-crystal display shown in Fig. 2 with device 1B by back light system 50, polaroid 22, liquid crystal display 10 and polaroid 20 stack gradually the image-display units 1 that forms, become liquid-crystal display device visuognosis side polaroid 20 upper surface setting resin layer 32, at the touch panel 30 of the upper surface setting of resin layer 32, form at the resin layer 31 of the upper surface setting of touch panel 30 and the protection panel 40 arranging in its surface.In addition, protection panel 40 has light shielding part 41 along the neighboring of this protection panel.

It should be noted that; the liquid-crystal display of Fig. 2 is with in device; between these two between image-display units 1 and touch panel 30 and between touch panel 30 and protection panel 40, all there is resin layer, but as long as resin layer exists in their at least one party.In addition, when touch panel is On-cell, touch panel and liquid crystal display are integrated.As its concrete example, the liquid crystal display 10 that can enumerate the liquid-crystal display device of Fig. 1 is replaced as the device that On-cell obtains.

According to the liquid-crystal display device shown in Fig. 1 and 2, because the cured article that possesses Photocurable resin composition of the present invention is as resin layer 31 or 32, therefore can obtain there is shock-resistance, without ghost image, the clear and high image of contrast gradient.

Liquid crystal display 10 can use the unit being made up of liquid crystal material well-known in the art.In addition, according to the control method of liquid crystal material, can be divided into TN (Twisted Nematic, twisted-nematic) mode, STN (Super-twisted nematic, supertwist is to row) mode, VA (Virtical Alignment, vertical orientated) mode, IPS (In-Place-Switching switches in face) mode etc., but in the present invention, can be the liquid crystal display that has used arbitrary control method.

As polaroid 20 and 22, can use common polaroid in the art.The processing such as antireflection, antifouling, hard painting can also be passed through in the surface of these polaroids.This surface treatment can be implemented to the one side of polaroid or to its two sides.

As touch panel 30, can use the conventional touch panel of the art.

Resin layer 31 or 32 for example can form with the thickness of 0.02mm～3mm.The particularly Photocurable resin composition of present embodiment, it is effectively that thick film is formed, and forms resin layer 31 more than 0.1mm or within 32 o'clock, is preferred.

As protection panel 40, can use common optics transparency carrier.

As this optics transparency carrier, for example, can enumerate the resin sheets such as the resin substrates such as the substrate, acrylic panel, polycarbonate plate of the inorganics such as sheet glass, quartz plate, thick polyester sheet.While needing high surface hardness, the plate of preferred glass, vinylformic acid etc., more preferably sheet glass.

In addition, these optics can pass through the processing such as antireflection, antifouling, hard painting with the surface of transparency carriers.This surface treatment can be implemented the one or two sides of this substrate.In addition, this substrate can also be used in combination multiple.

In addition, in order to improve the contrast gradient etc. that shows image, on the protection panel 40 being formed by these substrates, be provided with the light shielding part 41 of frame shape with the width of regulation along the neighboring of this protection panel.This light shielding part 41 has the function of the unwanted photoresistance of image display panel periphery being broken, prevented the reduction of the demonstration grade causing because of light leak.

Formation to back light system 50 does not limit, and is conventionally made up of lighting means such as reflection means and lamp such as reflectors.These reflection means and lighting means can be applied common image and show by the known means that use in device.

[image shows the manufacture method with device]

Image of the present invention show with the manufacture method of device be the manufacture method that configures in opposite directions, makes Photocurable resin composition by thering is image-display units or the touch panel of image displaying part in their gap with the protection panel along neighboring with light shielding part and make the curing image demonstration use device of described liquid Photocurable resin composition; wherein; make liquid Photocurable resin composition of the present invention in described gap, and at least from described protection panel side carry out rayed make described Photocurable resin composition solidify.

The liquid-crystal display of for example Fig. 1 can be manufactured as follows with device 1A: image-display units 1 and the protection panel 40 along neighboring with light shielding part 41 are configured in opposite directions; make Photocurable resin composition of the present invention in their gap; at least carrying out rayed from this protection panel side solidifies above-mentioned Photocurable resin composition; form resin layer 32, manufacture thus.

In addition; the liquid-crystal display that is equipped with touch panel of Fig. 2 can be manufactured as follows with device 1B: image-display units 1, touch panel 30 and the protection panel 40 along neighboring with light shielding part 41 are configured in opposite directions; make Photocurable resin composition of the present invention at least between touch panel 30 and protection panel; at least carrying out rayed from this protection panel side solidifies above-mentioned Photocurable resin composition; form resin layer 31, manufacture thus.In addition, also can make Photocurable resin composition of the present invention between image-display units 1 and touch panel 30, similarly make this resin combination be solidified to form resin layer 32.

Here, manufacturing liquid-crystal display with Photocurable resin composition in the past while using device, the Photocurable resin composition that is for example equivalent to fill in the space of posterior components of the light shielding part 41 of the part of the P of Fig. 1 and 2 does not have sufficient light to arrive, hinder curing, and solidifying of the Photocurable resin composition of light shielding part periphery fully carried out, show the quality with device thereby greatly damage image, cause the reduction of reliability.

But show the manufacture method with device for image of the present invention, owing to having used the Photocurable resin composition of the present invention with excellent solidified nature, therefore in the time of irradiation ultraviolet radiation, not only can make the transmittance section of the part of the Q that is equivalent to Fig. 1 and 2 solidify, and can make near the posterior components (P part) of the ultraviolet light shielding part 41 of not direct irradiation this transmittance section (Q part) also solidify.Therefore, show the manufacture method with device according to image of the present invention, can the productivity image demonstration device of quality bills of materials excellence well.

In addition; as the method that makes Photocurable resin composition between above-mentioned, for example, can enumerate the method for fitting after using decollator to be coated with Photocurable resin composition on image-display units, touch panel or protection panel under vacuum (decompression) or normal atmosphere, separate the method for casting Photocurable resin composition in the space segment that certain intervals configures.It should be noted that, when casting Photocurable resin composition, can also image-display units and protection panel around formation partition wall.

Rayed for example can use UV irradiation equipment according to the mode substantially vertical with filled Photocurable resin composition from protection panel side irradiation ultraviolet radiation.

As exposure now, be preferably 500mJ/cm ²～5000mJ/cm ².In addition, exposure refers to that the illumination of the mensuration such as available ultraviolet luxmeter (ProductName " UV-M02 " (light-receiving device: UV-36), Orc company system) is multiplied by the value of irradiation time (second) gained.

The light source of using as uviolizing, for example, can enumerate low pressure mercury lamp, medium pressure mercury lamp, high voltage mercury lamp, metal halide lamp, LED lamp etc.Wherein preferred high voltage mercury lamp, metal halide lamp.

It should be noted that, when rayed, can side by side also use irradiation from the side with the irradiation from protection panel side.In addition, can also side by side heat duplexer that contains Photocurable resin composition etc. with rayed solidifies promoting.

Above the image of the Photocurable resin composition manufacture as can the application of the invention is shown and is illustrated with the liquid-crystal display device of one of device, but the image demonstration of Photocurable resin composition manufacture that can the application of the invention is not limited to liquid-crystal display device with device.For example can also be applied to plasma display (PDP), cathode tube (CRT), field-emitter display (FED), OLED display, 3D indicating meter, Electronic Paper etc.

Embodiment

Further specifically describe by the following examples the present invention, but the invention is not restricted to following embodiment.

First, carry out following explanation to having applied the image demonstration synthesis example of spendable Photocurable resin composition in device of the present invention.

It should be noted that, in following synthesis example, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are the values recording based on following methods.

(weight-average molecular weight (Mw), number-average molecular weight (Mn))

Use the gel permeation chromatography (GPC) taking tetrahydrofuran (THF) (THF) as solvent to carry out, determine taking polystyrene as reference material.GPC condition is below shown.

Metering equipment: HLC-8320GPC (ProductName, Tosoh Co., Ltd. system)

Analyze chromatographic column: TSKgel Super Multipore HZ-H (3 connections) (ProductName, Tosoh Co., Ltd.)

Guard column: TSK guard column Super MP (HZ)-H (ProductName, Tosoh Co., Ltd.)

Elutriant: THF

Measure temperature: 25 DEG C

(synthesis example 1)

(synthesizing of polyhutadiene methacrylic ester)

Possessing cooling tube, thermometer, whipping appts, in the reaction vessel of dropping funnel and air injection tube, add the α of 978.2 mass parts, ω-polybutadiene diol (Tso Tat Co., Ltd., Japan's system, trade(brand)name " Polybutadieneglycol G-3000 ", (1, 2-structural unit/1, 4 structural units) containing proportional=90/10, hydroxyl value=27mgKOH/g), as p methoxy phenol 0.5 mass parts of stopper, and as dibutyltin dilaurate (Tokyo Fine Chemical Co., Ltd. system of catalyzer, trade(brand)name " L101 ") 0.05 mass parts.Then, make air in reaction vessel flow while be warming up to after 70 DEG C, one side stirring at 70～75 DEG C drips equably methacrylic acid 2-isocyanato ethyl ester (Showa Denko K. K's system, trade(brand)name " Karenz MOI ") 20.3 mass parts with the time of 1 hour on one side and reacts.

When dropping finishes rear reaction 5 hours; the results verification that IR (infrared absorption analysis) measures disappears to isocyanic ester; finish reaction, obtained end and have the polyhutadiene methacrylic ester (weight-average molecular weight is 7,700) of methacryloyl.The mean value (average functional group number) of the methacryloyl of every 1 molecule of this polyhutadiene methacrylic ester is 0.5 (value of being calculated by feeding quantity).

(relatively synthesis example 1)

(synthesizing of hydrogenated butadiene polymer methacrylic ester)

In the reaction vessel that possesses cooling tube, thermometer, whipping appts, dropping funnel and air injection tube, add hydrogenated butadiene polymer glycol (Tso Tat Co., Ltd., Japan's system of 1045.7 mass parts, trade(brand)name " Polybutadieneglycol GI-3000 ", hydroxyl value=29mgKOH/g), as p methoxy phenol 0.5 mass parts of stopper and as dibutyltin dilaurate (East capital Fine Chemical Co., Ltd. system of catalyzer, trade(brand)name " L101 ") 0.05 mass parts.Then, make air in reaction vessel flow while be warming up to after 70 DEG C, one side stirring at 70～75 DEG C drips equably methacrylic acid 2-isocyanato ethyl ester (Showa Denko K. K's system, trade(brand)name " Karenz MOI ") 20.3 mass parts with the time of 1 hour on one side and reacts.

When dropping finishes rear reaction 5 hours; the results verification that IR (infrared absorption analysis) measures disappears to isocyanic ester; finish reaction, obtained end and have the hydrogenated butadiene polymer methacrylic ester (weight-average molecular weight is 7,700) of methacryloyl.The mean value (average functional group number) of the methacryloyl of every 1 molecule of this hydrogenated butadiene polymer methacrylic ester is 0.5 (value of being calculated by feeding quantity).

(relatively synthesis example 2)

(synthesizing of hydrogenated isoprene methacrylic ester)

In the reaction vessel that possesses cooling tube, thermometer, whipping appts, dropping funnel and air injection tube, add C-terminal hydrogenated isoprene (Idemitsu Kosen Co., Ltd.'s system of 843.3 mass parts, trade(brand)name " エポー Le ", hydroxyl value=51mgKOH/g), as p methoxy phenol 0.5 mass parts of stopper and as dibutyltin dilaurate (East capital Fine Chemical Co., Ltd. system of catalyzer, trade(brand)name " L101 ") 0.05 mass parts.Then, make air in reaction vessel flow while be warming up to after 70 DEG C, one side stirring at 70～75 DEG C drips equably methacrylic acid 2-isocyanato ethyl ester (Showa Denko K. K's system, trade(brand)name " Karenz MOI ") 20.3 mass parts with the time of 1 hour on one side and reacts.

When dropping finishes rear reaction 5 hours; the results verification that IR (infrared absorption analysis) measures disappears to isocyanic ester; finish reaction, obtained end and have the hydrogenated isoprene methacrylic ester (weight-average molecular weight is 7,700) of methacryloyl.The mean value (average functional group number) of the methacryloyl of every 1 molecule of this hydrogenated isoprene methacrylic ester is 0.5 (value of being calculated by feeding quantity).

(relatively synthesis example 3)

(synthesizing of propylene glycol acrylate [PPGUA])

In the reaction vessel that possesses cooling tube, thermometer, whipping appts, dropping funnel and air injection tube, add polypropylene glycol (molecular weight is 2,000) 155 mass parts, vinylformic acid 2-hydroxy methacrylate 17.9 mass parts, as p methoxy phenol 0.5 mass parts of stopper and as dibutyltin dilaurate 0.05 mass parts of catalyzer.Then, make air flow and be warming up to after 70 DEG C on one side in reaction vessel, at 70～75 DEG C, stir one side on one side and drip equably 2,2,4-trimethyl hexamethylene diisocyanate, 32.4 mass parts with the time of 2 hours and react.

When dropping finishes rear reaction 5 hours, the results verification that IR (infrared absorption analysis) measures disappears to isocyanic ester, finish reaction, obtain the propylene glycol acrylate [PPGUA] (weight-average molecular weight is 7,000) that there is polypropylene glycol and trimethyl hexamethylene diisocyanate and have as repeating unit, two ends ethylenic unsaturated link(age).The mean value of the ethylenic unsaturated link(age) number of every 1 molecule of this propylene glycol acrylate is 2.0 (values of being calculated by feeding quantity).

(embodiment 1～8, comparative example 1～9)

Coordinate (A)～(D) composition according to the proportioning shown in table 1 and table 2, be uniformly mixed, prepared the Photocurable resin composition of embodiment 1～8 and comparative example 1～9.In addition, in table 1 and 2, (A)～(D) unit of the numerical value of composition is mass parts (solids component ratio).

In addition the compound using as the each composition in table 1 and 2, is as follows.

(A1) composition

" synthesis example 1 ": the polyhutadiene methacrylic ester obtaining in synthesis example 1.

(A1) the replacement compound of composition

" relatively synthesis example 1 ": the hydrogenated butadiene polymer methacrylic ester relatively obtaining in synthesis example 1.

" UC-102 ": Kuraray Co., Ltd. system, trade(brand)name.Shown in following general formula (a), there is methacryloyl and there is the compound (n=2 in following general formula (a), number-average molecular weight are 17,000) of the structural unit that comes from polyisoprene.

" relatively synthesis example 2 ": the hydrogenated isoprene methacrylic ester relatively obtaining in synthesis example 2.

" relatively synthesis example 3 ": the propylene glycol acrylate relatively obtaining in synthesis example 3.

(A2) composition

" RICON156 ": CRAY VALLEY company system, trade(brand)name.Polybutadiene homopolymer (number-average molecular weight is 1400).

(B) composition

" FA-314A ": Hitachi Chemical Co., Ltd.'s system, trade(brand)name.R in above-mentioned general formula (1) ¹for hydrogen atom, R ²for the mean value of nonyl, the n compound (Mw:452) that is 4.

(B) alternative compounds of composition

" FA-512AS ": Hitachi Chemical Co., Ltd.'s system, trade(brand)name.Vinylformic acid two cyclopentenes oxygen base ethyl esters.

" FA-318A ": Hitachi Chemical Co., Ltd.'s system, trade(brand)name.R in above-mentioned general formula (1) ¹for hydrogen atom, R ²for the mean value of nonyl, the n compound that is 8.

" ACMO ": acryloyl morpholine.

" EHA ": 2-EHA.

" LA ": lauryl acrylate.

(C) composition

" PE1 ": Showa Denko K. K's system, trade(brand)name.Tetramethylolmethane four shown in following formula (c1) (3-sulfydryl butyric ester).

" BD1 ": Showa Denko K. K's system, trade(brand)name.Isosorbide-5-Nitrae shown in following formula (c2)-bis-(3-sulfydryl butyryl acyloxy) butane.

" NR1 ": Showa Denko K. K's system, trade(brand)name.Shown in following formula (c3) 1,3,5-tri-(3-sulfydryl butyryl acyloxy ethyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones.

(D) composition

" TPO ": BASF AG's system.2,4,6-trimethylbenzoyl-diphenyl phosphine oxide (maximum absorption wavelength is 380nm).

To the resin combination obtaining in each embodiment and each comparative example and solidified obtain clear sheet carried out test shown below.The results are shown in table 1 and 2.

(viscosity)

Use E type viscometer (Toki Sangyo Co., Ltd.'s system, ProductName " RE-80L "), 3 ° of cone rotors, with 0.5min ^-1measure the viscosity (mPas) of the resin combination obtaining in each embodiment and each comparative example at 25 DEG C.

(consistency)

The resin combination obtaining in each embodiment and each comparative example is filled in vial, by Visual Confirmation consistency, evaluates according to following standard.

A: resin combination be transparent, consistency is good.

F: resin combination deposits yields gonorrhoea, consistency are poor.

(transmittance at wavelength 440nm place)

In PET (polyethylene terephthalate) film (Toyo Boseki K.K's system, ProductName " A4100 ", 86mm × 56mm × 100 μ is the upper resin combination obtaining in each embodiment and each comparative example that drips m), and the mode that reaches 175 μ m according to the thickness after the solidifying of this resin combination is across the spacer of 175 μ m another same PET film of fitting.Then, use UV irradiation equipment (Orc company system, ProductName " ELM-3000B-6N ") to irradiate 2,000mJ/cm from a side's wherein PET film side ²ultraviolet ray, make resin combination solidify, made clear sheet (cured article).

Baseline using PET duplex as transmissivity, peel PET film from 3 layer laminates (PET film/cured article/PET film) of gained, use spectrophotometer (Shimadzu Scisakusho Ltd's system, ProductName " UV-2400PC ") to measure the transmittance at the wavelength 440nm place of remaining cured article.

In addition, for the value of the transmittance at measured 400nm place, evaluate according to following standard.

A: the transmittance at wavelength 440nm place is more than 98%, transmittance is good.

F: the transmittance less than 98% at wavelength 440nm place, transmission rate variance.

(specific refractory power)

In PET (polyethylene terephthalate) film (Toyo Boseki K.K's system, ProductName " A4100 ", 86mm × 56mm × 100 μ is the upper resin combination obtaining in each embodiment and each comparative example that drips m), and the mode that reaches 350 μ m according to the thickness after the solidifying of this resin combination is across the spacer of 350 μ m another same PET film of fitting.Then, use UV irradiation equipment (Orc company system, ProductName " ELM-3000B-6N ") to irradiate 2,000mJ/cm from a side's wherein PET film side ²ultraviolet ray, make resin combination solidify, made clear sheet (cured article).

Peel PET film from 3 layer laminates (PET film/cured article/PET film) of gained, use ABBE index meter (Atago of Co., Ltd. system, ProductName " DR-M2 ") to measure 25 DEG C of remaining cured article, the specific refractory power at wavelength 589nm place.

(specific inductivity when frequency 1MHz)

The circular frame of the silicon rubber that to place diameter and be 50mm, thickness on demoulding PET film be 2mm, fill therein the resin combination obtaining in each embodiment and each comparative example, cover PET film thereon, use UV irradiation equipment (Orc company system, ProductName " ELM-3000B-6N ") to irradiate 1J/cm ²ultraviolet ray, make resin combination solidify, made transparent film (cured film).Specific inductivity when use dielectric medium is measured the frequency 1MHz that uses electrode special " HP16451B " and " HP4275A " (ProductName, the Precision LCR processed Meter of HEWLETT PACKARD company) to measure this transparent film.

(light shielding part solidifies width)

The resin combination obtaining in each embodiment and each comparative example is added drop-wise on 16 inches of square glass substrates, and the mode that reaches 175 μ m according to thickness is across the spacer of 175 μ m another 16 inches of square glass substrates of fitting.Then, use UV irradiation equipment (Orc company system, ProductName " ELM-3000B-6N ") to irradiate 2,000mJ/cm from a side's wherein glass substrate side ²ultraviolet ray, make resin combination solidify, made test film (cured article).In addition, now, the black ceramic that is 0% with the transmittance of wavelength 200～800nm in the glass-based plate side of uviolizing side forms the light shielding part of 8cm × 16cm, is arranged on the face of resin combination side.

Afterwards, the glass of a side of stripping test sheet, has fully formed the width of film with the resin combination that vernier callipers is measured light shielding part part, solidify width using this numerical value as light shielding part.This numerical value is larger, represents that the solidified nature at light shielding part place is more excellent.

As shown in Table 1, the Photocurable resin composition of embodiment 1～8 have suitable viscosity, consistency also good, light shielding part solidify width also for 40mm is above, the solidified nature excellence at light shielding part place.In addition, the transmittance of the cured article of this resin combination, specific refractory power and specific inductivity are all good.

On the other hand, as shown in Table 2, curing the failing at the light shielding part place of the Photocurable resin composition of comparative example 1～4,6～9 carried out fully.In addition, the result of the Photocurable resin composition of comparative example 5～9 is that the transmittance of consistency cured article poor, that obtained by this resin combination is also poor.

Utilizability in industry

The solidified nature excellence at the light shielding part place of Photocurable resin composition of the present invention, there is suitable viscosity, consistency is good.Therefore, Photocurable resin composition of the present invention can show and use with the material that possesses the space segment between protection panel and the image-display units etc. of light shielding part in device for being filled in along neighboring preferably as image.

Nomenclature

1A, 1B liquid-crystal display device

1 image-display units

10 liquid crystal displays

20,22 polaroids

30 touch panels

31,32 resin layers

40 protection panels

41 light shielding parts

50 back light systems

Claims

1. a Photocurable resin composition, it contains:

(A) there is the compound of the structural unit that comes from polyhutadiene;

(B) compound shown in following general formula (1);

(D) Photoepolymerizationinitiater initiater,

Wherein, as (A) composition, contain the compound that (A1) has (methyl) acryl and have the structural unit that comes from polyhutadiene,

In general formula (1), R ¹represent hydrogen atom or methyl, R ²represent the alkyl that hydrogen atom or carbon number are 1～12, n represents 1～7 number,

R in general formula (II) ³and R ⁴represent independently that respectively hydrogen atom or carbon number are 1～5 alkyl, q represents 0～3 integer, and * represents bonding part.

2. Photocurable resin composition according to claim 1, wherein, (C) composition is the mercaptan compound shown in following general formula (2),

R in general formula (2) ³and R ⁴represent independently that respectively hydrogen atom or carbon number are 1～5 alkyl, p represents 1～6 integer, and q represents 0～3 integer, and A represents the organic group of p valency.

3. Photocurable resin composition according to claim 1 and 2, wherein, in described general formula (1), R ²that carbon number is 4～12 alkyl.

4. according to the Photocurable resin composition described in any one in claim 1～3, it does not contain in fact organic solvent, and the viscosity of described Photocurable resin composition at 25 DEG C is 500～5000mPas.

5. according to the Photocurable resin composition described in any one in claim 1～4, wherein, (C) content of composition is with respect to (A)～(C) total amount of composition is 3～30 quality %.

6. according to the Photocurable resin composition described in any one in claim 1～5, wherein, content (A1) is 25～100 quality % with respect to the total amount of (A) composition.

7. according to the Photocurable resin composition described in any one in claim 1～6; wherein; as (A) composition, further contain the compound that (A2) do not have (methyl) acryl and have the structural unit that comes from polyhutadiene.

8. Photocurable resin composition according to claim 7, wherein, (A1) i.e. (A1) of mass ratio of composition and (A2) composition/(A2) is 25/75～95/5.

9. according to the Photocurable resin composition described in any one in claim 2～8, wherein, the A in described general formula (2) be following formula (C-1) or (C-2) shown in group or the carbon number alkylidene group that is 1～12,

Formula (C-1) or (C-2) in, * represents bonding part, X ¹～X ⁷representing independently respectively singly-bound or can having substituent carbon number is 1～12 alkylidene group.

10. according to the Photocurable resin composition described in any one in claim 1～9, wherein, (B) content of composition is with respect to (A)～(C) total amount of composition is 1～40 quality %.

11. according to the Photocurable resin composition described in any one in claim 1～10, and wherein, (A) content of composition is with respect to (A)～(C) total amount of composition is 50～98 quality %.

12. 1 kinds of image demonstration devices, it is the image demonstration device with stepped construction, described stepped construction comprises:

There is the image-display units of image displaying part;

There is the protection panel of light shielding part along neighboring; And

Wherein, described resin layer is the cured article of the Photocurable resin composition described in any one in claim 1～11.

13. 1 kinds of image demonstration devices, it is the image demonstration device with stepped construction, described stepped construction comprises:

There is the image-display units of image displaying part;

Touch panel;

There is the protection panel of light shielding part along neighboring; And

14. 1 kinds of images show the manufacture method with device; it is that the protection panel that has image-display units or the touch panel of image displaying part and have light shielding part along neighboring is configured in opposite directions, made Photocurable resin composition in their gap and makes the curing image of described Photocurable resin composition show the manufacture method with device

Wherein, make in claim 1～11 Photocurable resin composition described in any one in described gap, and at least carry out rayed from described protection panel side described Photocurable resin composition is solidified.