CN108137762A - Actinic energy ray curable resion composition and its manufacturing method - Google Patents

Actinic energy ray curable resion composition and its manufacturing method Download PDF

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Publication number
CN108137762A
CN108137762A CN201680060847.6A CN201680060847A CN108137762A CN 108137762 A CN108137762 A CN 108137762A CN 201680060847 A CN201680060847 A CN 201680060847A CN 108137762 A CN108137762 A CN 108137762A
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methyl
based compound
energy ray
propenoic
ray curable
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谷口亮辅
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Mitsubishi Kasei Corp
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Nippon Synthetic Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
    • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
    • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen

Abstract

As will not occur through when viscosity change, excellent storage stability, the actinic energy ray curable resion composition that may be suitably used to adhesive composition, coating agent composition, a kind of actinic energy ray curable resion composition is provided, it is characterized in that, it contains following (A), (B) and (X), as following (B), contain hydroxyl monomer (b1).(A) (methyl) propenoic methyl carbamate based compound.(B) ethylenically unsaturated monomer in addition to above-mentioned (A).(X) metal salt.

Description

Actinic energy ray curable resion composition and its manufacturing method
Technical field
The present invention relates to actinic energy ray curable resion composition, more specifically, be related to by through when it is caused viscous Degree variation is considerably less, excellent storage stability, may be suitably used to adhesive composition, the active-energy of coating agent composition is penetrated Line hardening resin composition.
Background technology
All the time, actinic energy ray curable resion composition by the active energy beam of very short time irradiate and Curing is completed, therefore can be widely used as smears, adhesive, bonding agent or anchor coating agent in various base materials etc.. (methyl) propenoic methyl carbamate, photopolymerization monomer, simultaneously are compounded in above-mentioned actinic energy ray curable resion composition Preferably further compounding Photoepolymerizationinitiater initiater situation it is more, wherein (methyl) propenoic methyl carbamate because have softness and can To obtain the characteristic of tough film etc. rather than usually use.Particularly, for (methyl) acrylic-amino of main chain for straight-chain Formic acid esters, the application in adhesive composition, coating agent composition receive expectation.
For example, for the adhesive used in the optical components such as the Optical devices such as touch screen, optical record medium, although Transparent bonding sheet is used, but due to comprising with printing height difference etc. in touch screen etc. in the purposes for pasting optical component The component of difference in height, therefore in such use excellent height is it is also desirable to have other than requiring bonding sheet that there is bonding force The poor tracing ability of degree.Make the thickness of adhesive phase thickening or using tool as assigning the means of difference in height tracing ability, having studied There is the situation of the adhesive phase of flexibility, therefore, use (methyl) propenoic methyl carbamate of relatively high molecular weight.
Manufacture (methyl) propenoic methyl carbamate has a various methods, but as commonly used approach, can enumerate as Lower method：(1) diisocyanate, glycol, hydroxyl (methyl) acrylate and the method (example for reacting it are disposably put into Such as, referring to patent document 1 with 2.)；(2) diisocyanate is made to be reacted with glycol, after obtaining compound containing terminal isocyanate group, This is made to contain terminal isocyanate group compound and the method for hydroxyl (methyl) acrylate reactions etc. (for example, referring to patent text Offer 3 and 4.).
In addition, usually when manufacturing (methyl) propenoic methyl carbamate, urged for reaction purpose is promoted using various Agent, wherein, the activity of urethane catalysts is high, thus usually using organo-tin compound.
Existing technical literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2013-56966 bulletins
Patent document 2：Japanese Unexamined Patent Publication 2014-5368 bulletins
Patent document 3：Japanese Unexamined Patent Publication 2011-162770 bulletins
Patent document 4：Japanese Unexamined Patent Publication 2002-309185 bulletins
Invention content
Problems to be solved by the invention
However, above-mentioned (1), (2) manufacturing method in, if (methyl) propenoic methyl carbamate weight average molecular weight increase Greatly；It, can in addition, if the quantity of amino-formate bond increases as caused by the urethane reaction of diisocyanate and glycol Reaction efficiency is reduced due to the viscosity in system steeply rises.As a result, as there are the unreacted isocyanic acids of denier The state of ester group, hydroxyl, therefore as time goes by, the molecular weight increase of (methyl) propenoic methyl carbamate, i.e. generation by Through when caused viscosity rise, go wrong in terms of storage stability.As a result, for its adhesive has been used to combine Object, smears, desired bonding physical property, Physical properties of coating film etc. can not be obtained by leading to the problem of.
Therefore, as inhibiting to pass through the method that caused viscosity rises by the time, first, the inventors discovered that for pole Power reduces the residual quantity of unreacted isocyanate group and largely the active energy ray-curable resin containing hydroxyl monomer Composition.
However, for the above-mentioned actinic energy ray curable resion composition largely containing hydroxyl monomer, although suppression Made through when viscosity rise, but can generate later the viscosity of composition through when reduce as new problem.
Therefore, the present invention in this context, its purpose is to provide will not occur through when viscosity change, preserve it is steady Qualitative actinic energy ray curable resion composition that is excellent, may be suitably used to adhesive composition, coating agent composition And its manufacturing method.
The solution to the problem
However, the present inventor has made intensive studies in view of the foregoing, as a result, it has been found that：For (first has been applied in combination Base) propenoic methyl carbamate based compound and hydroxyl monomer actinic energy ray curable resion composition, as (first Base) propenoic methyl carbamate based compound, it, can be with by using following (methyl) propenoic methyl carbamate based compound Obtain through when excellent storage stability actinic energy ray curable resion composition, it is so as to complete the present invention, described (methyl) propenoic methyl carbamate based compound has used when carrying out its manufacture and has been generally not used for manufacture (methyl) acrylic acid The metal salt of urethane compound is as catalyst.
That is, the first purport of the present invention is a kind of actinic energy ray curable resion composition, which is characterized in that it contains There are (methyl) propenoic methyl carbamate based compound (A), ethylenically unsaturated monomer (B) and metal salt in addition to above-mentioned (A) (X), as above-mentioned ethylenically unsaturated monomer (B) containing hydroxyl monomer (b1), in addition, its manufacturing method is the second purport.
The effect of invention
The actinic energy ray curable resion composition obtained in the present invention is made by containing following (A), (B) and (X) Be following (B) containing hydroxyl monomer (b1), so as to by through when caused viscosity change is considerably less, excellent storage stability, because This may be suitably used to adhesive composition, coating agent composition.
(A) (methyl) propenoic methyl carbamate based compound.
(B) ethylenically unsaturated monomer in addition to above-mentioned (A).
(X) metal salt.
It is if in addition, unsaturated single relative to above-mentioned (methyl) propenoic methyl carbamate based compound (A) and above-mentioned olefinic 100 parts by weight of total of body (B), the content of above-mentioned metal salt (X) is 1 × 10-3~1 × 10-1Parts by weight then further subtract It is few by through when caused viscosity change.
Moreover, if above-mentioned (methyl) propenoic methyl carbamate based compound (A) is that have except (methyl) acryloxy In ester bond other than ester bond and at least one of carbonic acid ester bond key (methyl) propenoic methyl carbamate based compound, then may be used With preferably obtain by through when few, excellent storage stability the such present invention of caused viscosity change effect.
In addition, if (methyl) acryloyl group equivalent of above-mentioned (methyl) propenoic methyl carbamate based compound (A) is 5000~100000, then soft cured coating film can be obtained, and then as suitable range of viscosities, therefore become operability Easily.
It is if in addition, unsaturated single relative to above-mentioned (methyl) propenoic methyl carbamate based compound (A) and above-mentioned olefinic 100 parts by weight of total of body (B), the content of above-mentioned hydroxyl monomer (b1) are 20~70 parts by weight, then make viscosity through when it is steady It is qualitative further excellent.
Moreover, if above-mentioned (methyl) propenoic methyl carbamate based compound (A) is multicomponent isocyanate based compound (a1), the reactant of hydroxyl (methyl) acrylate based compound (a2), polyalcohol based compound (a3), then can be preferably Obtain as through when caused viscosity change is few, of the invention as excellent storage stability effect.
In addition, if above-mentioned polyalcohol based compound (a3) is at least the one of polyester-based polyols and polycarbonate-based polyalcohol Person is then easy to get the effect of the present invention, and versatility becomes excellent.
If above-mentioned metal salt (X) is the fatty acid metal salts of carbon number 8~10, plays suitable catalytic capability and make reaction Property becomes excellent.
Moreover, if the manufacturing method of following actinic energy ray curable resion composition, wherein, the active-energy Ray-curable resin combination contains following (A), (B) and (X), contains hydroxyl monomer (b1), the side as following (B) Method is to make multicomponent isocyanate based compound (a1), hydroxyl (methyl) acrylic ester chemical combination in the presence of metal salt (X) Object (a2), polyalcohol based compound (a3) reaction obtain (methyl) propenoic methyl carbamate based compound (A), then can obtain To by through when caused viscosity change is considerably less, actinic energy ray curable resion composition of excellent storage stability.
(A) (methyl) propenoic methyl carbamate based compound.
(B) ethylenically unsaturated monomer in addition to above-mentioned (A).
(X) metal salt.
If relative to 100 parts by weight of (methyl) propenoic methyl carbamate based compound (A) obtained above, to become 5 ×10-3~1 × 10-1The mode of parts by weight is compounded above-mentioned metal salt (X), then can obtain further reduce by through when it is caused The actinic energy ray curable resion composition of viscosity change.
Specific embodiment
The present invention is described in detail below, but these embodiments are to show an example of desired embodiment Son.
It should be noted that in the present invention, (methyl) acrylic acid refers to acrylic or methacrylic acid, (methyl) propylene Acids refers to acrylic compounds or methacrylic, and (methyl) acryloyl group refers to acryloyl group or methylacryloyl, (first Base) acrylate refers to acrylate or methacrylate.In addition, acrylic resin is to instigate at least to contain a kind of (first Base) acrylate monomer polymeric composition polymerization obtained from resin.
The actinic energy ray curable resion composition of the present invention contains (methyl) propenoic methyl carbamate system chemical combination Object (A), ethylenically unsaturated monomer (B) and metal salt (X), the present invention in maximum be characterized in that containing metal salt (X).It is right below Each ingredient for forming the actinic energy ray curable resion composition of the present invention illustrates.
(metal salt (X))
As above-mentioned metal salt (X), preferably：The fatty acid salt of the metals such as tin, bismuth, zinc, titanium, such as can enumerate：Octanoic acid Tin, capric acid tin, neodecanoic acid tin, tin laurate, myristic acid tin, stearic acid tin, Bismuth Octoate, capric acid bismuth, bismuth neodecanoate, lauric acid Bismuth, zinc octoate, capric acid zinc, zinc neodecanoate, zinc laurate, sad titanium, capric acid titanium, neodecanoic acid titanium, lauric acid titanium etc..They can be with It is used alone or in combination of two or more.Wherein, preferably the fatty acid metal salts of carbon number 8~10, because reactivity it is excellent And the fatty acid salt of the carbon number 8~10 of particularly preferred tin or bismuth, particularly preferably tin octoate, capric acid tin, neodecanoic acid tin, octanoic acid Bismuth, capric acid bismuth, bismuth neodecanoate.
Relative to aftermentioned (methyl) propenoic methyl carbamate based compound (A) and the total of ethylenically unsaturated monomer (B) 100 parts by weight, the content of above-mentioned metal salt (X) is preferably 1 × 10-3~1 × 10-1Parts by weight, particularly preferably 2 × 10-3~8 ×10-2Parts by weight, further preferably 3 × 10-3~6 × 10-2Parts by weight.
Above-mentioned content has viscosity reduction tendency easy to perform when excessive, there is (methyl) propenoic methyl carbamate system when very few Close the tendency that the molecular weight of object (A) is easily reduced.
Above-mentioned metal salt (X) can be as catalysis when manufacturing (methyl) propenoic methyl carbamate based compound (A) The metal salt of agent compounding, can also be independently of (methyl) propenoic methyl carbamate based compound (A), ethylenically unsaturated monomer (B) and as the metal salt of individual compounding ingredients compounding, in addition it can be the metal salt both being combined with, from can shorten From the aspect of manufacturing time, preferably when manufacturing (methyl) propenoic methyl carbamate based compound (A) as catalyst The metal salt of compounding.
((methyl) propenoic methyl carbamate based compound (A))
(methyl) the propenoic methyl carbamate based compound (A) used in the present invention can enumerate：Make polynary isocyanic acid The substance that ester based compound (a1), hydroxyl (methyl) acrylate based compound (a2) reaction form, makes multicomponent isocyanate The object that based compound (a1), hydroxyl (methyl) acrylate based compound (a2) and polyalcohol based compound (a3) reaction form Matter, but preferably make multicomponent isocyanate based compound (a1), hydroxyl (methyl) acrylate based compound in the present invention (a2) and polyalcohol based compound (a3) reacts (methyl) the propenoic methyl carbamate based compound formed.
In addition, for (methyl) the propenoic methyl carbamate based compound (A) used in the present invention, from being easy to get this From the aspect of The effect of invention, preferably：With in ester bond (except the ester bond in (methyl) acryloyl group) and carbonic acid ester bond (methyl) propenoic methyl carbamate compound of at least one key.
As above-mentioned multicomponent isocyanate based compound (a1), such as can enumerate：Toluene di-isocyanate(TDI), diphenylmethyl Alkane diisocyanate, more phenylmethane polyisocyanates, modified diphenylmethane diisocyanate, xyxylene diisocyanate The aromatic systems polyisocyanic acid such as ester, tetramethyl xylylene diisocyanate, phenylene vulcabond, naphthalene diisocyanate Ester；Pentamethylene diisocyanate, hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, lysine two are different The fatty families polyisocyanates such as cyanate, lysine triisocyanate；Ester ring type system diisocyanate is (for example, isophorone Bis- (isocyanate group) hexamethylenes of diisocyanate, hydrogenated diphenyl methane diisocyanate, 1,3-, the bis- (isocyanates of 1,4- Base) hexamethylene, norbornene diisocyanate etc.) etc. ester ring types system polyisocyanates or these polyisocyanates trimerization Body compound or polymer compounds；Allophanic acid ester type polyisocyanates, biuret form polyisocyanates etc..
They can be used alone or two or more is applied in combination.
Wherein, from the viewpoint of xanthochromia is few, it is preferable to use：Pentamethylene diisocyanate, hexa-methylene diisocyanate The fatty families diisocyanate such as ester, trimethyl hexamethylene diisocyanate, lysine diisocyanate；Hydrogenated diphenyl first Bis- (isocyanate group) hexamethylenes of alkane diisocyanate, 1,3-, bis- (isocyanate group) hexamethylenes of 1,4-, two isocyanide of isophorone The ester ring types system such as acid esters, norbornene diisocyanate diisocyanate, from the aspect of cure shrinkage is small, particularly preferably makes With ester ring type system diisocyanate, (particularly isophorone diisocyanate, hydrogenated diphenyl methane diisocyanate, 1,3- are bis- (isocyanate group) hexamethylene, Isosorbide-5-Nitrae-bis- (isocyanate group) hexamethylene), from the aspect of reactivity and versatility are excellent, Further preferably use：Bis- (isocyanate group) hexamethylenes of 1,3-, isophorone diisocyanate.
As above-mentioned hydroxyl (methyl) acrylate based compound (a2), such as can enumerate：(methyl) acrylic acid 2- Hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 4- hydroxyl fourths (methyl) hydroxyalkyl acrylates such as ester, the own ester of (methyl) acrylic acid 6- hydroxyls；2- hydroxyethyls acryloyl phosphate, 2- (methyl) acryloyl-oxyethyl -2- hydroxypropyls phthalic acid ester, caprolactone modification (methyl) acrylic acid 2- hydroxy methacrylates, two Propylene glycol (methyl) acrylate, fatty acid modified-(methyl) glycidyl acrylate, polyethyleneglycol (methyl) acrylic acid Ester, (methyl) acrylic acid 2- hydroxy methacrylates, 2- hydroxyls -3- (methyl) acryloxypropyl (methyl) acrylate, glycerine Single (methyl) acrylate, glycerine two (methyl) acrylate, 2- hydroxyls -3- acryloyl groups-oxygroup propyl methacrylate, Pentaerythrite three (methyl) acrylate, caprolactone modification pentaerythrite three (methyl) acrylate, ethylene-oxide-modified season penta Tetrol three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, caprolactone modification dipentaerythritol five (methyl) Acrylate, ethylene-oxide-modified dipentaerythritol five (methyl) acrylate etc..
They can be used alone or two or more is applied in combination.
Wherein, from the aspect of the flexibility of adhesive phase is excellent, contain hydroxyl preferably with 1 ethylenically unsaturated group Base (methyl) acrylate based compound further preferably uses：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 2- Hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyls, (methyl) acrylic acid 4- hydroxybutyls, the own ester of (methyl) acrylic acid 6- hydroxyls It is special from the aspect of reactivity and versatility are excellent Deng (methyl) hydroxyalkyl acrylates, glycerine list (methyl) acrylate It is preferable to use (methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 4- hydroxybutyls, glycerine list (methyl) acrylate.
As above-mentioned polyalcohol based compound (a3), such as can enumerate：Polyether system polyalcohol, gathers polyester-based polyols Carbonic ester system polyalcohol, polyolefin polyalcohol, (methyl) acrylic acid series multiple alcohol, polysiloxane series polyalcohol etc..They can To be used alone or in combination of two or more.
As polyether system polyalcohol, such as can enumerate：Polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polytetramethylene The polyether system polyalcohol containing alkylen structures such as base glycol, polyhexamethylene glycol, these polyalkylene glycol random or Block copolymer etc..
As polyester-based polyols, such as can enumerate：The condensation polymer of polyalcohol and polybasic carboxylic acid, cyclic ester (lactone) Ring-opening polymerization polymer, reactant based on polyalcohol, polybasic carboxylic acid and cyclic ester this 3 kinds of ingredients etc..
As above-mentioned polyalcohol, such as can enumerate：Ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, trimethylene Glycol, 1,4- tetramethylene glycols, 1,3- tetramethylene glycols, 2- methyl-1s, 3- trimethylenes, 1,5- pentamethylenes two Alcohol, neopentyl glycol, 1,6- hexamethylene glycols, 3- methyl-1s, 5- pentamethylenes glycol, 2,4- diethyl -1,5- pentamethylenes Glycol, glycerine, trimethylolpropane, trimethylolethane, cyclohexane diol class (1,4- cyclohexane diols etc.), bisphenols are (double Phenol A etc.), glycitols (xylitol, sorbierite etc.) etc..
As above-mentioned polybasic carboxylic acid, for example,：Malonic acid, maleic acid, fumaric acid, succinic acid, glutaric acid, oneself two The aliphatic dicarboxylic acids such as acid, suberic acid, azelaic acid, decanedioic acid, dodecanedioic acid；The ester ring types dicarboxyl such as 1,4- cyclohexane dicarboxylic acids Acid；The aromatic series such as terephthalic acid (TPA), M-phthalic acid, phthalic acid, 2,6 naphthalene dicarboxylic acid, terephthalic acid (TPA), trimellitic acid Dicarboxylic acids etc..
As above-mentioned cyclic ester, for example,：Propiolactone, Beta-methyl-δ-valerolactone, 6-caprolactone etc..
As polycarbonate-based polyalcohol, such as can enumerate：The reactant of polyalcohol and phosgene, cyclic carbonate are (sub- Alkyl carbonate etc.) ring-opening polymerization polymer etc..
As above-mentioned polyalcohol, exemplary polyalcohol etc. in the explanation of aforementioned polyester-based polyols can be enumerated, as Above-mentioned alkylene carbonate, such as can enumerate：Ethylene carbonate, trimethylene carbonate, tetramethylene carbonic ester, six methylenes Base carbonic ester etc..
It should be noted that as long as polycarbonate-based polyalcohol has carbonic acid ester bond in the molecule and end is hydroxyl Compound, with carbonic acid ester bond while, can also be with ester bonds.
As polyolefin polyalcohol, can enumerate：Homopolymer or copolymer conduct with ethylene, propylene, butylene etc. Saturation hydrocarbon skeleton and its molecular end have hydroxyl polyalcohol.Such as it can enumerate：Polyisoprene system polyalcohol, poly- fourth Diene series polyalcohol, itrile group butadiene-based polyalcohol, styrene butadiene system polyalcohol etc..
Polyolefin polyalcohol, which can also be, makes all or part of ethylenically unsaturated group hydrogenation contained in its structure The hydrogenated polyolefin hydrocarbon system polyalcohol formed.
As (methyl) acrylic acid series multiple alcohol, point of the polymer or copolymer in (methyl) acrylate can be enumerated In son at least there is the polyalcohol of 2 hydroxyls, as above-mentioned (methyl) acrylate, such as can enumerate：(methyl) acrylic acid Methyl esters, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) Hexyl 2-propenoate, (first Base) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) decyl acrylate, (methyl) lauryl ester, (methyl) octadecyl ester etc. (methyl) alkyl acrylate etc..
As polysiloxane series polyalcohol, such as can enumerate：The poly- silica of dimethyl polysiloxane polyalcohol, aminomethyl phenyl Alkane polyalcohol etc..
Wherein, preferably：Polyester-based polyols, polyether system polyalcohol, polycarbonate-based polyalcohol, from being easy to get the present invention Effect and versatility it is excellent from the aspect of, particularly preferably polyester-based polyols, polycarbonate-based polyalcohol.
In addition, the hydroxyl number contained by polyalcohol based compound (a3) is preferably 2~5, particularly preferably 2~3, Further preferably 2.When hydroxyl number is excessive, have the tendency that gelation easily occurs in the reaction.
In the present invention, the weight average molecular weight of polyalcohol based compound (a3) is preferably 1000~20000, is particularly preferably 2000~18000, it is more preferably 3000~16000.When above-mentioned weight average molecular weight is too small, the bonding force for having adhesive phase drops Low tendency, reactivity when excessive with multicomponent isocyanate based compound (a1) reduce.
It should be noted that above-mentioned weight average molecular weight is the weight average molecular weight to be converted by standard polystyren molecular weight, It measures in the following way, in high performance liquid chromatography (Showa Denko K. K's system, " Shodex GPC system-11 types ") The middle column using 3 series connection：Shodex GPC KF-806L (exclusion limit molecular weight：2×107, separating ranges：100~2 × 107, theoretical cam curve：10000 column plates/root, filler material：Styrene diethylene benzene copoly mer, filler grain size：10μ m)。
As the hydroxyl value of above-mentioned polyalcohol based compound (a3), preferably 10~300mgKOH/g, particularly preferably 15~ 150mgKOH/g, further preferably 20~120mgKOH/g.When above-mentioned hydroxyl value is excessively high, there is (methyl) propenoic methyl carbamate The tendency that based compound (A) low molecule quantization and adhesive strength reduce when hydroxyl value is too low, has a high viscosity and workability reduces Tendency.
(methyl) the propenoic methyl carbamate based compound (A) used in the present invention can for example enumerate：It (1) will be aforementioned Multicomponent isocyanate based compound (a1), hydroxyl (methyl) acrylate based compound (a2), polyalcohol based compound (a3) Method that is disposable or making its reaction in input reactor respectively；(2) make multicomponent isocyanate based compound (a1) and more in advance First alcohol based compound (a3) reaction obtains reaction product, makes the reaction product and hydroxyl (methyl) acrylate based compound (a2) method of reaction etc., but the preferably method of (2) from the viewpoint of stability, reduction by-product of reaction etc..
Multicomponent isocyanate based compound (a1) can use well known reaction with reacting for polyalcohol based compound (a3) Means.It at this point, for example usually can be by by the isocyanate group in multicomponent isocyanate based compound (a1)：Polyalcohol system The molar ratio for closing the hydroxyl in object (a3) is set as 2n：(2n-2) (n is more than 2 integer) left and right, so as to be remained (methyl) propenoic methyl carbamate based compound containing terminal isocyanate of isocyanate group, can after obtaining the compound To carry out the addition reaction of hydroxyl (methyl) acrylate based compound (a2).
Above-mentioned multicomponent isocyanate based compound (a1) is made to react and be reacted with polyalcohol based compound (a3) in advance Product makes the addition reaction of the reaction product and hydroxyl (methyl) acrylate based compound (a2) that can also use well known Reaction means.
Molar ratio is reacted for reaction product and hydroxyl (methyl) acrylate based compound (a2), for example, polynary The isocyanate group of isocyanates based compound (a1) is 2, the hydroxyl of hydroxyl (methyl) acrylate based compound (a2) When being 1, reaction product：Hydroxyl (methyl) acrylate based compound (a2) is 1：2 or so, multicomponent isocyanate system chemical combination When the isocyanate group of object (a1) is 3, the hydroxyl of hydroxyl (methyl) acrylate based compound (a2) is 1, reaction production Object：Hydroxyl (methyl) acrylate based compound (a2) is 1：3 or so.
Addition reaction for the reaction product and hydroxyl (methyl) acrylate based compound (a2), by reacting The residual isocyanate base containing ratio of system terminates reaction at the time of becoming below 0.1 weight %, so as to obtain (first Base) propenoic methyl carbamate based compound (A).
Reaction temperature when carrying out above-mentioned reaction is usually 30~90 DEG C, preferably 40~80 DEG C, and the reaction time is usually 2 ~30 hours, preferably 3~20 hours.
Present invention it is preferred that：Metal salt is used when manufacturing (methyl) propenoic methyl carbamate based compound (A) (X) as catalyst, multicomponent isocyanate based compound (a1), hydroxyl (methyl) propylene are made in the presence of metal salt (X) Acid esters based compound (a2) and polyalcohol based compound (a3) reaction obtain (methyl) propenoic methyl carbamate based compound (A)。
As when manufacturing above-mentioned (methyl) propenoic methyl carbamate based compound (A) metal salt is used as catalyst (X) compounding amount when, relative to 100 parts by weight of (methyl) propenoic methyl carbamate based compound (A), preferably with become 5 × 10-3~1 × 10-1The mode of parts by weight is compounded, is particularly preferably 6 × 10-3~9 × 10-2Parts by weight, further preferably 7 × 10-3~8 × 10-2Parts by weight.
The molecular weight for when above mixing quantity is very few, having (methyl) propenoic methyl carbamate based compound (A) is easily reduced Tendency, have the tendency that easily promoting viscosity reduction when excessive.
Make multicomponent isocyanate based compound (a1), hydroxyl (methyl) acrylate based compound (a2) and more in manufacture It, as needed can be with during (methyl) the propenoic methyl carbamate based compound (A) that the reaction of first alcohol based compound (a3) forms Using the organic solvent without the functional group to react to isocyanate group, such as：The esters such as ethyl acetate, butyl acetate The organic solvents such as the aromatics such as the ketones such as class, methyl ethyl ketone, methyl iso-butyl ketone (MIBK), toluene, dimethylbenzene.
Furthermore it is also possible to use aftermentioned ethylenically unsaturated monomer (B) instead of above-mentioned organic solvent or with organic solvent combination As diluent.
In the present invention, viscosity is increased and is located when (methyl) propenoic methyl carbamate based compound (A) becomes high molecular weight Rationality is deteriorated, therefore it is preferable to use aftermentioned ethylenically unsaturated monomer (B) as diluent.
Thus (methyl) the propenoic methyl carbamate based compound (A) used in the present invention can be manufactured.
(methyl) acryloyl group equivalent of (methyl) propenoic methyl carbamate based compound (A) is preferably 5000~ 100000th, 6000~90000, further preferably 7000~80000, particularly preferably 8000~70000 are particularly preferably.On State (methyl) acryloyl group equivalent it is too low when, have the tendency that when being used as adhesive adhesive phase bonding force reduce, mistake Gao Shi, the viscosity with (methyl) propenoic methyl carbamate based compound (A) is excessively high and operation is made to become difficult.
The weight average molecular weight of (methyl) propenoic methyl carbamate based compound (A) is preferably 5000~200000, especially Preferably 6000~150000, it is more preferably 7000~120000, particularly preferably 8000~100000.It is above-mentioned it is heavy divide equally When son amount is too low, the bonding force with adhesive phase reduces, and when excessively high, has (methyl) propenoic methyl carbamate system chemical combination The viscosity of object (A) is excessively high and operation is made to become difficult tendency.
It should be noted that above-mentioned weight average molecular weight is the Weight-average molecular to be converted by standard polystyren molecular weight Amount, measures in the following way：In high performance liquid chromatography (Showa Denko K. K's system, " Shodex GPC system-11 Type ") the middle columns using 3 series connection：：Shodex GPC KF-806L (exclusion limit molecular weight：2×107, separating ranges：100 ~2 × 107, theoretical cam curve：10000 column plates/root, filler material：Styrene diethylene benzene copoly mer, filler grain Diameter：10μm).
In addition, the viscosity of (methyl) propenoic methyl carbamate based compound (A) is preferably with the viscosimeter at 60 DEG C 1000~10000000mPas, particularly preferably 2000~8000000mPas, further preferably 3000~ 6000000mPa·s.When above-mentioned viscosity is excessively high, have the tendency that operation becomes difficult, when too low, when having coating the control of film thickness become Obtain difficult tendency.
It should be noted that the measure of viscosity is carried out by E types viscosimeter.
(ethylenically unsaturated monomer (B))
In the present invention, as ethylenically unsaturated monomer (B), need containing hydroxyl monomer (b1).
As hydroxyl monomer (b1), such as can enumerate：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl) acrylic acid 4- Hydroxybutyl, (methyl) acrylic acid 5- hydroxyls pentyl ester, the own ester of (methyl) acrylic acid 6- hydroxyls, (methyl) acrylic acid 8- hydroxyls are pungent The carbon number 1 of the alkyl such as ester, (methyl) acrylic acid 10- hydroxyls last of the ten Heavenly stems ester, (methyl) acrylic acid (4- Hydroxymethyl-cyclo-hexyls) methyl esters~ (methyl) hydroxyalkyl acrylates of 16 (preferably 1~12), caprolactone modification (methyl) acrylic acid 2- hydroxy methacrylates etc. oneself Lactone-modified monomer, polyethyleneglycol (methyl) acrylate, (methyl) acrylic acid 2- hydroxy methacrylates, 2- acryloxy second Base -2- hydroxyethyls phthalic acid, N- methylols (methyl) acrylamide, N- hydroxyethyls (methyl) acrylamide etc. contain primary hydroxyl The olefinic unsaturated compound of base；(methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxybutyls, (methyl) propylene Sour 2- hydroxyls -3- phenoxy-propyls, (methyl) acrylic acid 3- chlorine-2-hydroxyls propyl ester, (methyl) acrylic acid 2- hydroxyl -3- phenoxy groups The olefinic unsaturated compound containing secondary hydroxyl such as propyl ester；(methyl) acrylic acid 2,2- dimethyl -2- hydroxy methacrylates etc. contain tert-hydroxyl Olefinic unsaturated compound.
Wherein, from viscosity and with acrylic resin it is excellent in compatibility, obtain readily from the aspect of, be (methyl) third Olefin(e) acid 2- hydroxy methacrylates, (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 2- hydroxyls Base butyl ester, further preferably (methyl) acrylic acid 4- hydroxybutyls.
In addition, they can be used alone or two or more is applied in combination.
It is whole relative to ethylenically unsaturated monomer (B), the content of above-mentioned hydroxyl monomer (b1) be preferably 40 weight % with Upper, particularly preferably more than 45 weight %, further preferably more than 50 weight %.
When above-mentioned content is very few, have the tendency that easily promoting thickening.
In addition, the total relative to (methyl) propenoic methyl carbamate based compound (A) and ethylenically unsaturated monomer (B) 100 parts by weight, the content of above-mentioned hydroxyl monomer (b1) be preferably 20~70 parts by weight, particularly preferably 20~65 parts by weight, Further preferably 25~60 parts by weight.
When above-mentioned content is excessive, have the tendency that easily promoting viscosity reduction when very few, have the tendency that easily promoting thickening.
Above-mentioned hydroxyl monomer (b1) can be another for (methyl) propenoic methyl carbamate based compound (A) The substance of row compounding can also be and is compounded when manufacturing (methyl) propenoic methyl carbamate based compound (A) as diluent Substance.
In addition, as ethylenically unsaturated monomer (B), the olefinic other than hydroxyl monomer (b1) can also be used unsaturated single Body (b2) (is also denoted as " ethylenically unsaturated monomer (b2) " sometimes below.), it, can be with as above-mentioned ethylenically unsaturated monomer (b2) It is any one of monofunctional monomer, bifunctional monomer, more than trifunctional monomer.
As monofunctional monomer, as long as the monomer containing 1 ethylenically unsaturated group, such as can enumerate：(first Base) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) third Enoic acid ter-butyl ester, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid nonyl Ester, (methyl) decyl acrylate, (methyl) isodecyl acrylate, (methyl) dodecylacrylate, (methyl) acrylic acid are just Stearyl ester, (methyl) isostearyl acrylate, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) third Olefin(e) acid tricyclodecyl, (methyl) acrylic acid dicyclopentenyl ester, (methyl) benzyl acrylate, phenolethylene oxide are modified (methyl) third Olefin(e) acid ester, nonyl phenol epoxy pronane modification (methyl) acrylate, (methyl) acrylic acid 2- methoxy acrylates, ethyl carbitol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, methoxyl group polypropylene glycol (methyl) acrylate, (first Base) acrylate, butoxy ethyl, acryloyl morpholine, n-vinyl pyrrolidone, 2- vinylpyridines, (methyl) acrylic acid contracting Water glyceride, 3- ethyl -3- oxetanyl methyls (methyl) acrylate, (methyl) acrylic acid chaff ester, (methyl) acrylic acid Tetrahydrochysene chaff ester, (2- methyl -2- ethyl -1,3- dioxolanes -4- bases) (methyl) methyl acrylate, hexamethylene spiral shell -2- (1,3- bis- Butyl oxide link -4- bases) (methyl) methyl acrylate, gamma-butyrolacton (methyl) acrylate, trimethylolpropane (dimethoxym ethane) (first Base) acrylate, styrene, vinyltoluene, chlorostyrene, α-methylstyrene, acrylonitrile, vinyl acetate, (methyl) Allyl acrylate, 2- (methyl) acryloyl-oxyethyl phosphate ester acid monoesters etc..
In addition, other than aforementioned monofunctional monomer, the Michael's addition object of acrylic acid or 2- propylene can be also enumerated Trimethylammonium dicarboxylic acid monoesters as the Michael's addition object of acrylic acid, such as can enumerate：Acrylic acid dimer, methyl Acrylic acid dimer, acrylic acid trimer, methacrylic acid trimer, acrylic acid tetramer, methacrylic acid tetramer etc..Separately Outside, it as the 2- acryloyl-oxyethyl dicarboxylic acid monoesters of the carboxylic acid with specific substituent group, such as can enumerate：2- propylene Trimethylammonium monomester succinate, 2- methacryloxyethyls monomester succinate, 2- acryloyl-oxyethyl phthalic acids Monoesters, 2- methacryloxyethyl phthalic acids monoesters, 2- acryloyl-oxyethyl hexahydrobenzene dioctyl phthalate monoesters, 2- methyl Acryloyl-oxyethyl hexahydrobenzene dioctyl phthalate monoesters etc..And then it can also enumerate oligoester acrylate.
As bifunctional monomer, as long as the monomer containing 2 ethylenically unsaturated groups, such as can enumerate：Two (methyl) acrylic acid glycol ester, two (methyl) acrylic acid binaryglycol esters, two (methyl) acrylic acid tetraethylene glycol esters, two (first Base) polyalkylene glycol acrylate ester, two (methyl) propylene acid propylene glycol esters, two (methyl) acrylic acid dipropylene glycol esters, two (methyl) It is acrylic acid polypropylene glycol ester, two (methyl) acrylic acid butanediol esters, two (methyl) acrylic acid neopentyl glycol ester, ethylene-oxide-modified Bisphenol A-type two (methyl) acrylate, epoxy pronane modification bisphenol A-type two (methyl) acrylate, 1,6-HD epoxy second Alkane is modified two (methyl) acrylate, 1,9- nonanediols two (methyl) acrylate, two (first of phthalic acid 2-glycidyl base ester Base) acrylate, 3-hydroxypivalic acid be modified two (methyl) acrylic acid neopentyl glycol ester, 2- (methyl) acryloyl-oxyethyl acid Phosphate diester etc..
As monomer more than trifunctional, as long as the monomer containing 3 or more ethylenically unsaturated groups, such as can It enumerates：Trimethylolpropane tris (methyl) acrylate, pentaerythrite four (methyl) acrylate, six (first of dipentaerythritol Base) acrylate, three (methyl) acryloyloxyethoxy trimethylolpropanes, ethylene-oxide-modified three acrylic acid of isocyanuric acid Ester, ethylene-oxide-modified dipentaerythritol six (methyl) acrylate, ethylene-oxide-modified pentaerythrite four (methyl) acrylic acid Ester, caprolactone modification dipentaerythritol six (methyl) acrylate, caprolactone modification pentaerythrite four (methyl) acrylate etc..
They can be used alone, two or more can also be applied in combination.
In above-mentioned ethylenically unsaturated monomer (b2), from the flexibility of film it is excellent from the aspect of, it is preferable to use simple function Monomer, from the aspect of and flexibility few from xanthochromia is excellent, particularly preferably：(methyl) methyl acrylate, (methyl) acrylic acid second Ester, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) heptylacrylate, (methyl) 2-ethyl hexyl acrylate, (methyl) acrylic acid nonyl ester, (methyl) decyl acrylate, (methyl) third Olefin(e) acid isodecyl ester, (methyl) dodecylacrylate, the positive stearyl ester of (methyl) acrylic acid, (methyl) isostearyl acrylate, (methyl) acrylic acid 2- methoxy acrylates, ethyl carbitol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylic acid Ester, methoxyl group polypropylene glycol (methyl) acrylate, (methyl) acrylate, butoxy ethyl.
Above-mentioned ethylenically unsaturated monomer (b2) is preferably used when manufacturing (methyl) propenoic methyl carbamate based compound (A) Make diluent.
(actinic energy ray curable resion composition)
Use above-mentioned (methyl) propenoic methyl carbamate based compound (A), ethylenically unsaturated monomer (B) and metal salt (X) actinic energy ray curable resion composition of the present invention can be obtained.
Containing ratio (the weight of (methyl) propenoic methyl carbamate based compound (A) and ethylenically unsaturated monomer (B) Than) it is usually (A)：(B)=80：20~20：80th, preferably (A)：(B)=75：25~25：75th, particularly preferably (A)：(B) =70：30~25：75th, further preferably (A)：(B)=65：35~30：70.
Ethylenically unsaturated monomer (B) relative to (methyl) propenoic methyl carbamate based compound (A) it is excessive when, have resin The viscosity of composition is too low and makes the thick tendency for applying and becoming difficult, when very few, has the viscosity of resin combination excessively high and make operation Become difficult tendency.
The actinic energy ray curable resion composition of the present invention is further preferred：Pass through activity to be effectively performed The curing of energy-ray and containing Photoepolymerizationinitiater initiater (C).
As above-mentioned Photoepolymerizationinitiater initiater (C), do not have as long as the polymerization initiator generated free radicals using the effect of light It is particularly limited to, such as can enumerate：Diethoxy acetophenone, 2- hydroxy-2-methyl -1- phenyl-propane -1- ketone, benzil two Methyl ketal, 4- (2- hydroxyl-oxethyls) phenyl-(2- hydroxyl -2- propyl) ketone, 1- hydroxycyclohexylphenylketones, 2- methyl -2- Morpholino (4- thiomethylphenyls) propane -1- ketone, 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls) butanone, 2- hydroxyls Base -2- methyl-1s-[4- (1- methyl ethylenes) phenyl] propane oligomer, 1- [4- (2- hydroxyl-oxethyls)-phenyl] -2- hydroxyls Base -2- methyl-1s-propane -1- ketone, 2- hydroxyls -1- { 4- [4- (2- hydroxy-2-methyls-propiono)-benzyl]-phenyl } -2- first The acetophenones such as base-propane -1- ketone；Benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether, benzoin isobutyl ether Etc. benzoin class；Benzophenone, o-benzoyl yl benzoic acid methyl esters, 4- phenyl benzophenones, 4- benzoyls -4 '-methyl-two Aralkyl sulfid, 3,3 ', 4,4 '-four (t-butyl peroxy carbonyl) benzophenone, 2,4,6- tri-methyl benzophenones, 4- benzoyls Base-N, N- dimethyl-N-[2- (1- oxo -2- propenyloxy groups) ethyl] benzyl ammonium bromide, (4- benzoylbenzyls) front three The benzophenones such as ammonium chloride；2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4- diethyl thioxanthones, 2,4- dichloros The chloro- 4- propoxythioxanthones of thioxanthones, 1-, 2- (3- dimethylamino -2- hydroxyls) -3,4- dimethyl -9H- thioxanthones -9- ketone The thioxanthene ketone class such as methochloride；2,4,6- trimethylbenzoy-diphenies phosphine oxide, bis- (2,6- dimethoxybenzoyls Base) acylphosphine oxide class such as -2,4,4- trimethyl-pentyls phosphine oxide, bis- (2,4,6- trimethylbenzoyls)-phenyl phosphine oxides Deng.It should be noted that these Photoepolymerizationinitiater initiaters (C) can be used alone or two or more is applied in combination.
In addition, the auxiliary agent as these Photoepolymerizationinitiater initiaters (C), such as can also be applied in combination：Triethanolamine, three isopropyls Hydramine, 4,4 '-dimethylamino benzophenone (michler's ketone), 4,4 '-diethylamino benzophenone, 2- dimethylaminoethyls Yl benzoic acid, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acids (n-butoxy) ethyl ester, 4- dimethylaminos Isoamyl benzoate, 4- dimethylaminobenzoic acid 2- ethylhexyls, 2,4- diethyl thioxanthones, 2,4- diisopropylthioxanthones Deng.These auxiliary agents can be used alone or two or more is applied in combination.
Relative to (methyl) propenoic methyl carbamate based compound (A) and 100 weight of total of ethylenically unsaturated monomer (B) Part is measured, the content of above-mentioned Photoepolymerizationinitiater initiater (C) is preferably 1~10 parts by weight, particularly preferably 2~5 parts by weight.Above-mentioned content When very few, there is curing rate reduction, curability can not be improved even if excessive, there is economy reduction.
In the actinic energy ray curable resion composition of the present invention, in addition to (methyl) propenoic methyl carbamate system Except conjunction object (A), ethylenically unsaturated monomer (B) and metal salt (X), Photoepolymerizationinitiater initiater as needed (C), do not damaging The present invention effect in the range of, can also contain antioxidant, fire retardant, antistatic agent, filler, levelling agent, stabilizer, Catalysts other than reinforcing agent, delustering agent, (X) etc..And then as crosslinking agent, can also use has by thermally-induced friendship The compound of the effect of connection, specifically：Epoxide, aziridine cpd, melamine compound, isocyanates chemical combination Object, chelate etc..
And then for the actinic energy ray curable resion composition of the present invention, from inhibiting, unreacted component, raising are viscous From the perspective of resultant force, multi-thioalcohol compound can be contained.
It as multi-thioalcohol compound, is not particularly limited, preferably there is the compound of 2~6 sulfydryls in the molecule, such as It can enumerate：The aromatic series such as the aliphatic polythiols such as two mercaptan of alkyl of carbon number 2~20 or so, two mercaptan of xyxylene are more Thio-alcohol, alcohols halohydrin addition product halogen atom replaced by sulfydryl polythiols, by polyepoxide chemical combination The polythiols of the vulcanization hydroformylation reaction product formation of object, polyalcohols and sulfydryl second by having 2~6 hydroxyls in the molecule Polythiols that the carboxylate of acid, β-mercaptopropionic acid or β-mercaptobutyric acid is formed etc., they can be used alone or combine Use two or more.
Relative to (methyl) propenoic methyl carbamate based compound (A) and 100 weight of total of ethylenically unsaturated monomer (B) Part is measured, the content of multi-thioalcohol compound is preferably 0.01~10 parts by weight, particularly preferably 0.1~5 parts by weight.
In addition, the actinic energy ray curable resion composition of the present invention is according to need in order to viscous when adjustment coats Degree, can also use：The alcohols such as methanol, ethyl alcohol, propyl alcohol, n-butanol, isobutyl；Acetone, methylisobutylketone, methyl ethyl ketone, cyclohexanone Wait ketones；The dioxanes such as ethyl cellosolve；The aromatics such as toluene, dimethylbenzene；The gylcol ethers such as propylene glycol monomethyl ether；Second The acetate esters such as sour methyl esters, ethyl acetate, butyl acetate；The retarder thinners such as diacetone alcohol, but have dissolvent residual in film, is dry The possibility that cure component plays when dry, therefore preferably contain substantially no solvent.
It should be noted that contain substantially no solvent refer to it is whole relative to actinic energy ray curable resion composition Body, usually below 1 weight %, preferably below 0.5 weight %, further preferably below 0.1 weight %.
The actinic energy ray curable resion composition obtained in the present invention on various base materials are coated on by going forward side by side It irradiates active energy beam after row is dry and cures.
It as the painting method of above-mentioned actinic energy ray curable resion composition, is not particularly limited, such as can arrange It enumerates：Injection, spray, dipping, roller, rotation, curtain, flowing, slit, mold, intaglio plate, comma, distributor, silk-screen printing, spray The wet coating method of ink print or the like.It is viscous for solid or height as above-mentioned actinic energy ray curable resion composition Painting method during liquid is spent, can enumerate and actinic energy ray curable resion composition is heated, drops its viscosity The hot melt coated after low using the above method.
As above-mentioned active energy beam, in addition to the light such as far ultraviolet, ultraviolet light, near ultraviolet ray, infrared ray, X ray, Except the electromagnetic waves such as gamma-rays, electron ray, proton radiation, neutron ray etc. can be used, is obtained from curing rate, irradiation unit Easness, price etc. consideration, the curing carried out by ultraviolet light irradiation is advantageous.It should be noted that it carries out Cure during electronbeam irradiation even if without using Photoepolymerizationinitiater initiater (C).
Make its cured method as by ultraviolet light irradiation, use the high pressure for the light for sending out 150~450nm wavelength regions Mercury lamp, ultrahigh pressure mercury lamp, carbon arc lamp, metal halide lamp, xenon lamp, chemical lamp, electrodeless discharge lamp, LED etc., progress 30~ 3000mJ/cm2The irradiation of left and right.
It can also be heated after ultraviolet light irradiation and be fully cured to realize as needed.
It, can for the base material of the object of actinic energy ray curable resion composition obtained in of the invention as coating It enumerates：Polyolefin-based resins, polyester based resin, polycarbonate-based resin, acrylonitrile butadient styrene (ABS), Polystyrene resin, polyamide etc., their molded product (film, piece, cup etc.), metal base (metal vapor deposition layer, gold Belong to plate (copper, stainless steel (SUS304, SUSBA etc.), aluminium, zinc, magnesium etc.)), glass etc., their composite base material.
Film thickness as cured coating film, it is often preferred that 1~300 μm, particularly preferably 2~250 μm, further preferably 5~200 μm.
The actinic energy ray curable resion composition obtained in the present invention is combined as adhesive composition, smears Object is highly useful.
The present inventor deduces：The catalyst used so far when manufacturing (methyl) propenoic methyl carbamate based compound It can remain in (methyl) propenoic methyl carbamate based compound, the carbamate in (methyl) propenoic methyl carbamate With hydroxyl monomer due to catalyst ester exchange reaction occurs for key, thus makes (methyl) propenoic methyl carbamate based compound Molecular weight reduce, as a result viscosity is caused timely to reduce.
In addition, it deduces：(methyl) propenoic methyl carbamate based compound has in ester bond and carbonic acid ester bond at least During a kind of key, at least one of ester bond and carbonic acid ester bond in (methyl) propenoic methyl carbamate based compound key are with containing hydroxyl Ester exchange reaction occurs for base monomer, and viscosity is made timely to reduce.Deep grind has been carried out on the basis of the mechanism of these suppositions Study carefully, so as to complete the present invention.
In addition, as described herein, it is believed that：The feelings of metal salt are used in actinic energy ray curable resion composition Under condition, compared with the situation of the big organo-metallic compound of the oxidation numbers such as dibutyl tin laurate, metallic atom is by electrical screen It covers, can deduce：As a result, amino-formate bond, ester bond, carbonic ester in (methyl) propenoic methyl carbamate based compound The interaction of key, the hydroxyl in hydroxyl monomer and metallic atom weakens, therefore is not easy to carry out ester decomposition reaction, thus can send out Wave as through when caused viscosity change is considerably less, of the invention as excellent storage stability effect.
Embodiment
It is exemplified below embodiment and more specific description is carried out to the present invention, but the present invention is without departing from the range of its purport Just it is not limited to the following embodiments.It should be noted that in example, " part ", " % " etc. represent weight basis.
＜ (methyl) propenoic methyl carbamate based compound (A) ＞
As described below, as (methyl) propenoic methyl carbamate based compound (A) manufacture (methyl) acrylic-amino Formic acid esters based compound (A-1)~(A-6).
(Production Example 1)
To have thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in input isophorone two it is different Cyanate (a1) 4.2g (0.019 mole), difunctionality polyester polyol (a3) (Mw=12000) 65.2g (0.016 mole), second Base carbitol acrylate (b2-1) 30g, tin octoate (X-1) 0.01g, the 2,6- bis- as polymerization inhibitor as catalysts Tertiary butyl cresols 0.04g after being reacted 10 hours at 70 DEG C, puts into acrylic acid 2- hydroxy methacrylates (a2) 0.6g (0.005 mole), It is reacted 6 hours at 60 DEG C.Terminate reaction at the time of residual isocyanate base becomes 0.1%, obtain (methyl) acrylic acid Urethane compound (A-1) (weight average molecular weight (Mw)；And the mixing of ethyl carbitol acrylate (b2-1) 74000) Object.
(Production Example 2)
To have thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in put into the bis- (isocyanic acids of 1,3- Ester group) hexamethylene (a1) 8.7g (0.045 mole), glycerin monomethyl acrylic ester (a2) 3.7g (0.022 mole), as reaction Tin octoate (X-1) 0.01g, 2, the 6- di-tert-butyl cresol 0.04g as polymerization inhibitor of catalyst, react 7 hours at 60 DEG C Afterwards, difunctionality polycarbonate polyol (a3) (Mw=7000) 87.6g (0.045 mole) is put into, is reacted 10 hours at 60 DEG C. Terminate reaction at the time of residual isocyanate base becomes 0.1%, obtain (methyl) propenoic methyl carbamate based compound (A-2) (weight average molecular weight (Mw)；16000).
(Production Example 3)
To have thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in put into the bis- (isocyanic acids of 1,3- Ester group) hexamethylene (a1) 8.7g (0.045 mole), glycerin monomethyl acrylic ester (a2) 3.7g (0.022 mole), as reaction It is small to react 7 at 60 DEG C by neodecanoic acid tin (X-2) 0.01g, 2, the 6- di-tert-butyl cresol 0.04g as polymerization inhibitor of catalyst Shi Hou puts into difunctionality polycarbonate polyol (a3) (Mw=7000) 87.6g (0.045 mole), and it is small that 10 are reacted at 60 DEG C When.Terminate reaction at the time of residual isocyanate base becomes 0.1%, obtain (methyl) propenoic methyl carbamate system chemical combination Object (A-3) (weight average molecular weight (Mw)；16000).
(Production Example 4)
To have thermometer, blender, water-cooled condenser, nitrogen mouth blown 4 mouthfuls of flasks in put into the bis- (isocyanic acids of 1,3- Ester group) hexamethylene (a1) 8.7g (0.045 mole), glycerin monomethyl acrylic ester (a2) 3.7g (0.022 mole), as reaction Bismuth Octoate (X-3) 0.01g, 2, the 6- di-tert-butyl cresol 0.04g as polymerization inhibitor of catalyst, react 7 hours at 60 DEG C Afterwards, difunctionality polycarbonate polyol (a3) (Mw=7000) 87.6g (0.045 mole) is put into, is reacted 10 hours at 60 DEG C. Terminate reaction at the time of residual isocyanate base becomes 0.1%, obtain (methyl) propenoic methyl carbamate based compound (A-4) (weight average molecular weight (Mw)；14000).
(Production Example 5)
In above-mentioned Production Example 1, catalysts are replaced with into dibutyl tin laurate (X'-1) 0.01g, except this with It is outer to be reacted using same method, obtain (methyl) propenoic methyl carbamate based compound (A-5) (weight average molecular weight (Mw)；And the mixture of ethyl carbitol acrylate (b2-1) 75000).
(Production Example 6)
In above-mentioned Production Example 2, catalysts are replaced with into dibutyl tin laurate (X'-1) 0.01g, except this with It is outer to be reacted using same method, obtain (methyl) propenoic methyl carbamate based compound (A-6) (weight average molecular weight (Mw)；16000).
＜ ethylenically unsaturated monomers (B) ＞
As ethylenically unsaturated monomer (B), prepare following substance.
(b1-1)：Acrylic acid 4- hydroxybutyls
(b2-1)：Ethyl carbitol acrylate
＜ Examples 1 to 5,1~3 ＞ of comparative example
Each compounding ingredients for manufacturing, preparing in a manner described are compounded in a manner of becoming the content ratio shown in table 1 below (A) it and (B) and is equably mixed, obtains actinic energy ray curable resion composition.
The active energy ray-curable tree obtained in above-described embodiment 1~5, comparative example 1~3 is had rated in the following manner Oil/fat composition.Show the result in table 1.
(ageing stability)
Actinic energy ray curable resion composition is stood 10 days in 60 DEG C of drying machines, has carried out ageing stability Experiment.Viscosimetric analysis is carried out to testing front and rear each sample, rate of change in viscosity is calculated by its radiometer, has carried out storage stability Evaluation.For the temperature of viscosimetric analysis, embodiment 1,2 and Comparative Examples 1 and 2 carry out at 20 DEG C, embodiment 3~5 and comparative example 3 carry out at 60 DEG C.It should be noted that viscosimetric analysis using E types viscosimeter (Toki Sangyo Co., Ltd.'s system, VISCOMETER TPE-100H types) it carries out.
(evaluation criteria)
Zero ... rate of change in viscosity is for 95% less than 105%
× ... rate of change in viscosity is less than 95% or is more than 105%
[table 1]
Numerical value in (note) () is compounding parts by weight.
According to above-mentioned evaluation result, (methyl) the propenoic methyl carbamate system chemical combination of metal salt manufacture is utilized for using The actinic energy ray curable resion composition of Examples 1 to 5 obtained from object, through when viscosity change it is small and preserve steady It is qualitative excellent.
In contrast, for it is using all the time, contain use dibutyl tin laurate manufacture (methyl) propylene The actinic energy ray curable resion composition of the comparative example 1,3 of sour carbamate, occur through when viscosity reduce, supplying A problem that product state labile occurs when practicality.
In addition, the actinic energy ray curable resion composition of the comparative example 2 for not containing hydroxyl monomer, generates Through when viscosity rise, when for practicality occur product state labile a problem that.
Above embodiment illustrates the concrete mode in the present invention, but above-described embodiment is only example, is not used in restriction Property explain.Those skilled in the art will appreciate that various deformations are included within the scope of the invention.
Industrial availability
It is combined by the use of the actinic energy ray curable resion composition that the manufacturing method of the present invention obtains as adhesive Object, coating agent composition, especially as optical component with or optical thin film adhesive composition, coating agent composition right and wrong Chang Youyong's.It particularly can steadily make (methyl) propenoic methyl carbamate based compound of high molecular weight, therefore can be with It is suitably used for the adhesive of durability, impact resistance and the excellent optical component stickup of difference in height tracing ability.

Claims (10)

1. a kind of actinic energy ray curable resion composition, which is characterized in that it contains following (A), (B) and (X), as Following (B) containing hydroxyl monomer (b1),
(A) (methyl) propenoic methyl carbamate based compound,
(B) ethylenically unsaturated monomer in addition to (A),
(X) metal salt.
2. actinic energy ray curable resion composition according to claim 1, which is characterized in that relative to described 100 parts by weight of total of (methyl) propenoic methyl carbamate based compound (A) and the ethylenically unsaturated monomer (B), it is described The content of metal salt (X) is 1 × 10-3~1 × 10-1Parts by weight.
3. the actinic energy ray curable resion composition according to claim 1 or 2, which is characterized in that (first Base) propenoic methyl carbamate based compound (A) is ester bond and carbon in addition to the ester bond in (methyl) acryloxy (methyl) propenoic methyl carbamate based compound of at least one of acid esters key key.
4. actinic energy ray curable resion composition described in any one of claim 1 to 3, which is characterized in that (methyl) the acryloyl group equivalent of (methyl) the propenoic methyl carbamate based compound (A) is 5000~100000.
5. actinic energy ray curable resion composition according to any one of claims 1 to 4, which is characterized in that Relative to (methyl) the propenoic methyl carbamate based compound (A) and 100 weight of total of the ethylenically unsaturated monomer (B) Part is measured, the content of the hydroxyl monomer (b1) is 20~70 parts by weight.
6. actinic energy ray curable resion composition according to any one of claims 1 to 5, which is characterized in that (methyl) the propenoic methyl carbamate based compound (A) is multicomponent isocyanate based compound (a1), hydroxyl (methyl) The reactant of acrylate based compound (a2), polyalcohol based compound (a3).
7. actinic energy ray curable resion composition according to claim 6, which is characterized in that the polyalcohol system Compound (a3) is at least one of polyester-based polyols and polycarbonate-based polyalcohol.
8. actinic energy ray curable resion composition according to any one of claims 1 to 7, which is characterized in that The metal salt (X) is the fatty acid metal salts of carbon number 8~10.
A kind of 9. manufacturing method of actinic energy ray curable resion composition, which is characterized in that the active energy beam Hardening resin composition contains following (A), (B) and (X), contains hydroxyl monomer (b1), the method as following (B) In, multicomponent isocyanate based compound (a1), hydroxyl (methyl) acrylate based compound are made in the presence of metal salt (X) (a2), polyalcohol based compound (a3) reaction obtains (methyl) propenoic methyl carbamate based compound (A),
(A) (methyl) propenoic methyl carbamate based compound,
(B) ethylenically unsaturated monomer in addition to (A),
(X) metal salt.
10. the manufacturing method of actinic energy ray curable resion composition according to claim 9, which is characterized in that Relative to 100 parts by weight of (methyl) propenoic methyl carbamate based compound (A) described in obtaining, to become 5 × 10-3~1 × 10-1The mode of parts by weight is compounded the metal salt (X).
CN201680060847.6A 2015-12-22 2016-12-21 Actinic energy ray curable resion composition and its manufacturing method Pending CN108137762A (en)

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