CN104981525B - active energy ray-curable coating composition - Google Patents

active energy ray-curable coating composition Download PDF

Info

Publication number
CN104981525B
CN104981525B CN201480007642.2A CN201480007642A CN104981525B CN 104981525 B CN104981525 B CN 104981525B CN 201480007642 A CN201480007642 A CN 201480007642A CN 104981525 B CN104981525 B CN 104981525B
Authority
CN
China
Prior art keywords
methyl
compound
acrylate
coating composition
active energy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201480007642.2A
Other languages
Chinese (zh)
Other versions
CN104981525A (en
Inventor
小仓绢子
北村昭宪
古田尚正
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toagosei Co Ltd
Original Assignee
Toagosei Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toagosei Co Ltd filed Critical Toagosei Co Ltd
Publication of CN104981525A publication Critical patent/CN104981525A/en
Application granted granted Critical
Publication of CN104981525B publication Critical patent/CN104981525B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08F290/068—Polysiloxanes
    • 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
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
    • 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
    • C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
    • C08F230/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal
    • C08F230/08—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon
    • C08F230/085—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing a metal containing silicon the monomer being a polymerisable silane, e.g. (meth)acryloyloxy trialkoxy silanes or vinyl trialkoxysilanes
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • 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
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/442—Block-or graft-polymers containing polysiloxane sequences containing vinyl polymer sequences

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Paints Or Removers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

The active energy ray-curable coating composition of the present invention contains following (A) (C) composition with special ratios.(A)：Organo-silicon compound, by the silicon compound (a1) 1mol, SiY that represent with respect to formula (1) containing (methyl) acryloyl group4The ratio hydrolytie polycondensation of silicon compound (a2) 0.3～1.8mol that (Y generate for siloxanes key group) represents and obtain.(B)：(methyl) acrylate mixture; it is made up of carabamate adducts (b1) and (methyl) acrylate (b2) derived from aliphatic polyol more than trivalent respectively; carabamate adducts (b1) are that have more than 2 (methyl) acryloyl groups and have the additive reaction of more than 1 hydroxyl (methyl) acrylate and polyisocyanates and obtain, and (methyl) acrylate (b2) is that have more than 3 (methyl) acryloyl groups and do not have hydroxyl (methyl) acrylate.(C)：Intramolecular has the free-radical polymerised unsaturated compound of nitrogen-atoms.

Description

Active energy ray-curable coating composition
Technical field
The present invention relates to active energy ray-curable coating composition, belong to active energy ray-curable compositionss and coating Technical field.
Background technology
In recent years, using glass in the display such as the just rapid touch screen popularized or smart mobile phone, but for lightweight With prevent glass during breakage from dispersing, studying instead of plastics.
In general, the light weight of plastic basis material, impact resistance and easy formability etc. are excellent, but surface easily scratches, hardness Low, have the shortcomings that significantly to damage outward appearance when therefore directly using.Therefore, the table of plastic basis material is usually applied with coating composition Face, carries out so-called hard conating process, gives wearability and marresistance etc..
For conventional coating composition, it is used in solvent, being dissolved with the coating composition of resin, is coated in It is dried after on base material and forms resin film, but in order to improve productivity etc., also studying Photocurable composition and thermosetting always The property changed compositionss.
Here, as the hard varnish putting on plastic basis material it is proposed that the hard varnish of ultra-violet solidified acrylic compounds, heat Hard varnish of curable silicone system etc..
Although the wearability of the hard varnish of the silicon-type of Thermocurable and excellent scratch resistance, there is problems with：Gu Change time length, productivity are poor, and need high temperature sometimes to produce substrate deformation etc. because during solidification.In contrast to this, ultraviolet is solid The general wearability of the hard varnish of acrylic compounds of the property changed and marresistance are poor, but hardening time is short, productivity is excellent.
As described above, the hard varnish of ultra-violet solidified acrylic compounds is with respect to heat-curable composition, from productivity and section Excellent from the viewpoint of energy, in order to play this speciality, carried out the insufficient performance of raising the wearability of cured film and The research of marresistance.
For example, as it is known that have coordinating silica sol or cooperation to have the silicon of (methyl) acryloxy in the composition The method of hydride compounds.
Specifically, it was known that having the alkoxy silane that containing silica sol, there is (methyl) acryloxy and propylene The ultraviolet-curable coating compositionss (patent documentation 1) of acid esters, have containing alkoxy silane and the intramolecular containing isocyanates There is the reactant of polyfunctional acrylic ester of hydroxyl and more than 3 acryloyl groups, have multifunctional the third of more than 3 acryloyl groups The ultraviolet-curable coating compositionss (patent documentation 2) of olefin(e) acid ester and silica sol.
But, these coating compositions compared with conventional ultraviolet-curable coating compositionss although cured film resistance to Mill property and excellent scratch resistance, but both wearability and marresistance can not be met simultaneously, or there is no satisfaction in practicality Performance.In addition, different according to the base material being used, adaptation is insufficient sometimes.
In this regard, as wearability, marresistance and the hard varnish excellent with the adaptation of base material etc., applicant proposed containing There is the photo-curable coating composition (patent documentation 3) of specific organo-silicon compound.
Patent documentation 1:Special public affairs table clear 57-500984 publication
Patent documentation 2:JP 5-287215 publication
Patent documentation 3:JP 2011-88996 publication
Content of the invention
Invention problem to be solved
However, the photo-curable coating composition described in patent documentation 3 applies for the viscosity of regulation composition, imparting Adaptive is it is necessary to adopt organic solvent.Thus, for example in situation carrying out thick film coating etc., solvent flower is sometimes distilled off Time-consuming, there is room for improvement.
In general, in the case that replacement organic solvent complex reaction monomer etc. is to adjust composition viscosity, due to The hardness of solidfied material and marresistance decline, and the cured film obtaining can not be fully satisfactory as hard conating.Therefore, seek Ask solvent-free system, meet hardness and marresistance, by the curable coating group of the activation-energy-ray such as electron ray, ultraviolet Compound.
In addition, in general, have the unsaturated chemical combination of long-chain segment by cooperation intramolecular in solidification compound Thing, the Tg of solidfied material reduces, impact resistance improves.But, such cured film is declined due to crosslink density, there is hardness and resistance to The tendency of scratch resistance decline.Therefore, seeking can obtain meeting hardness and marresistance and the also excellent solidification of impact resistance The solidification compound of film.
The problem of the present invention is the active energy ray-curable coating composition providing without organic solvent, and this activation energy is penetrated The viscosity of line curable coating composition is sufficiently reduced to coatable degree, when being applied to the base materials such as plastics, its cured film Show sufficient hardness and marresistance.
In addition, the problem of the present invention is to provide active energy ray-curable coating composition, its viscosity is sufficiently reduced to can The degree of coating, when being applied to the base materials such as plastics, its cured film shows sufficient hardness and marresistance, and impact resistance Also excellent.
Means to solve the problem
The present inventor etc. have made intensive studies to solve above-mentioned problem, it was found that having by using containing The compositionss of the compound of nitrogen-atoms and free-radical polymerised unsaturated group, even if do not use the organic solvent can be by compositionss yet Adjust to can abundant coating viscosity, can get the solidfied material of hardness and excellent scratch resistance.In addition, the present inventor etc. finds, By using containing the compound with isocyanuric acid system ring (イ ソ シ ア ヌ Le) and free-radical polymerised unsaturated group Compositionss, can get that hardness is high, marresistance and the also excellent cured film of impact resistance, so far complete the present invention.
The present invention is as described below.
[1] active energy ray-curable coating composition, contains：
(A) organo-silicon compound, it is the silicon compound containing (methyl) acryloyl group by making following formulas (1) represent (a1) silicon compound (a2) being represented with following formulas (2) is closed according to respect to 1 mole of above-mentioned silication of above-mentioned silicon compound (a1) Thing (a2) is that 0.3～1.8 mole of ratio is hydrolyzed obtained from polycondensation,
[changing 1]
(in formula (1), R1For the alkyl of carbon number 1～6, the aralkyl of carbon number 7～10 or carbon number 6～10, there is aryl Organic group, R2For the divalent saturated hydrocarbyl of carbon number 1～6, R3For hydrogen atom or methyl, X is hydrolization group, but multiple X that This is identical or different, and n is 0 or 1)
SiY4···(2)
(in formula (2), Y generates group for siloxanes key, and multiple Y can be same to each other or different to each other)
(B) (methyl) acrylate mixture, it is by carabamate adducts (b1) and (methyl) acrylate (b2) Constitute, carabamate adducts (b1) be by trivalent more than aliphatic polyol derived from, there are more than 2 (methyl) propylene The additive reaction of acyl group and (methyl) acrylate and polyisocyanates with more than 1 hydroxyl obtains, (methyl) propylene Acid esters (b2) be by trivalent more than aliphatic polyol derived from, there are more than 3 (methyl) acryloyl groups and there is no hydroxyl (methyl) acrylate,
And
(C) in addition to mentioned component (A) and mentioned component (B), intramolecular have nitrogen-atoms free-radical polymerised not Saturated compoundss,
The content of mentioned component (A), mentioned component (B) and mentioned component (C) with them when adding up to 100 weight portion, Mentioned component (A) is 5～50 weight portions, mentioned component (B) is 30～90 weight portions, mentioned component (C) is 5～35 weight portions.
[2] active energy ray-curable coating composition described in above-mentioned [1], wherein, above-claimed cpd (a1) is formula (1) compound that the X in is 0 for alkoxyl and n,
Above-claimed cpd (a2) is the compound for alkoxyl for the Y in formula (2).
[3] active energy ray-curable coating composition described in above-mentioned [1] or [2], wherein, mentioned component (C) contains At least one compound (C1) selected from monomer containing morpholinyl, amide-containing monomer and lactam compound.
[4] active energy ray-curable coating composition described in above-mentioned [3], wherein, above-claimed cpd (C1) be selected from Acryloyl morpholine, at least one of N- vinyl formamide, N- vinyl acetamide and N- vinyl-Epsilon-caprolactam.
[5] active energy ray-curable coating composition described in any one of above-mentioned [1]～[4], wherein, mentioned component (C) contain the compound (C2) with isocyanuric acid system ring, the content of this compound (C2) is 5～30 weight portions.
[6] active energy ray-curable coating composition described in above-mentioned [5], wherein, above-claimed cpd (C2) is by ring Oxygen alkane or the free-radical polymerised unsaturated compound of caprolactone modification.
[7] active energy ray-curable coating composition described in any one of above-mentioned [1]～[6], wherein, by mentioned component (A), when, mentioned component (B) and mentioned component (C) total is set to 100 weight portion, the content of mentioned component (C) is 10～35 weights Amount part, mentioned component (C) contains at least one chemical combination selected from monomer containing morpholinyl, amide-containing monomer and lactam compound Thing (C1) and the compound (C2) with isocyanuric acid system ring, when both total is set to 10～35 weight portion, above-mentioned chemical combination The content ratio of thing (C1) is 5～30 weight portions, and the content ratio of above-claimed cpd (C2) is 5～30 weight portions.
Invention effect
The compositionss of an embodiment of the present invention can make the compositionss without organic solvent, can be formed with respect to moulding For the various base materials such as material, there is the also excellent cured film of high hardness, marresistance.
In addition, the compositionss of the other embodiment according to the present invention, can be formed and come with respect to the various base material such as plastics Say that there is the also excellent cured film of high hardness, marresistance and impact resistance.
Specific embodiment
The active energy ray-curable coating composition of the present invention contains mentioned component (A), (B) and (C), with respect to them Total 100 weight portions,
(A) composition 5～50 weight portion,
(B) composition 30～90 weight portion, and
(C) composition 5～35 weight portion.
Hereinafter, each composition and compositionss are described in detail.
It is explained, in this specification, acryloyl group or methylacryloyl are expressed as " (methyl) acryloyl group ", will Acrylate or methacrylate are expressed as " (methyl) acrylate ".
1. composition (A)
The composition (A) of the present invention is the silicon compound containing (methyl) acryloyl group by making following formulas (1) represent (a1) silicon compound (a2) (hereinafter referred to as " compound that (hereinafter referred to as " compound (a1) ") and following formulas (2) represent (a2) ") be 0.3～1.8 mole with respect to compound (a1) 1 mole compound (a2) ratio hydrolytie polycondensation obtained from have Organic silicon compound.
[changing 1]
(in formula (1), R1For the alkyl of carbon number 1～6, the aralkyl of carbon number 7～10 or carbon number 6～10, there is aryl Organic group, R2For the divalent saturated hydrocarbyl of carbon number 1～6, R3For hydrogen atom or methyl, X is hydrolization group, but multiple X that This is identical or different, and n is 0 or 1)
SiY4···(2)
(in formula (2), Y generates group for siloxanes key, and multiple Y can be same to each other or different to each other)
In the formula (1) representing compound (a1), R1For the alkyl of carbon number 1～6, the aralkyl of carbon number 7～10 or carbon The organic group with aryl of number 6～10.
Wherein, the alkyl of preferred carbon number 1～6, from the viewpoint of the excellent in abrasion resistance of the cured film of the compositionss obtaining, More preferably methyl.
R2For the divalent saturated hydrocarbyl of carbon number 1～6, preferably alkylidene.As alkylidene, from the solidification of the compositionss obtaining From the viewpoint of the excellent in abrasion resistance of film, cost of material, more preferably trimethylene.R3For hydrogen atom or methyl.
X is hydrolization group, and multiple X can be same to each other or different to each other.As hydrolization group, as long as having water-disintegrable Group, can adopt various groups.Hydrogen atom, alkoxyl, cycloalkyloxy, aryloxy group and alkoxy aryl specifically can be enumerated.Its In, preferably alkoxyl, the more preferably alkoxyl of carbon number 1～6.As the concrete example of alkoxyl, can enumerate methoxyl group, ethyoxyl, Propoxyl group, butoxy, amoxy and hexyloxy etc..
In addition, n is 0 or 1, from the viewpoint of the excellent in abrasion resistance of the cured film of the compositionss obtaining, preferably 0.
In formula (1), the n as preferred compound is 0 and X is the concrete example of the compound of alkoxyl, can enumerate 2- (first Base) acryloyl-oxyethyl triethoxysilane, 3- (methyl) acryloxypropyl trimethoxy silane and 3- (methyl) third Alkene acryloxypropylethoxysilane ethyl triethoxysilane etc..
In the formula (2) representing compound (a2), Y generates group, the multiple siloxanes keys in 1 molecule for siloxanes key Generate group can be same to each other or different to each other.
Generate group, preferably alkoxyl as siloxanes key.As the preference of alkoxyl, methoxyl group, ethoxy can be enumerated The alkoxyl of the carbon numbers such as base, positive propoxy, isopropoxy, n-butoxy and sec-butoxy 1～4.
The preferred concrete example of compound (a2) is four positive propoxy silane, trimethoxy-positive propoxy silane, dimethoxy Base two-positive propoxy silane, methoxyl group three-positive propoxy silane etc. have the alkoxysilane compound containing trialkylsilyl group in molecular structure of positive propoxy.
Alkoxysilane compound containing trialkylsilyl group in molecular structure containing positive propoxy both can be a kind of compound or have positive propoxy, tool There is the mixture of the compound of other alkoxyls.
The mixture of the alkoxysilane compound containing trialkylsilyl group in molecular structure containing positive propoxy both can be used in mixed way Multiple components it is also possible to directly Exchange the compound manufacturing using by alcohol.For example, it is possible to by making that above-mentioned formula (2) represents in 1- propanol and not having The silicon compound (for example, tetramethoxy-silicane) of positive propoxy occurs alcohol exchange reaction to obtain.Alternatively, it is also possible to directly use The product being obtained by this reaction.
Composition (A) be by by compound (a1) and compound (a2) with respect to compound (a1) 1 mole compound (a2) it is that 0.3～1.8 mole of ratio is hydrolyzed obtained from polycondensation (hereinafter referred to as " the 1st operation ").It is explained, hydrolysis The reaction condition of polycondensation is not particularly limited, preferably alkalescence condition, below, the 1st operation under alkalescence condition is described.
With regard to the reaction ratio of compound (a1) and compound (a2), with respect to 1 mole of compound (a1), compound (a2) Ratio be 0.3～1.8 mole, the ratio of preferred compound (a2) is 0.8～1.6 mole, the more preferably ratio of compound (a2) Example is 1～1.4 mole.By being reacted with this ratio, can in the case of the gelation after the neutralization reaction that do not react effectively Manufacture composition (A).
By carrying out above-mentioned 1st operation in the basic conditions, reacted gelation can be prevented, can be with high yield system Cause point (A).
Specifically, the pH of reaction system is the value more than 7, preferably pH is more than 8 to alkalescence condition, and more preferably pH is more than 9. It is explained, the upper limit is usually pH13.By making reaction system be above-mentioned pH, excellent storage stability can be manufactured with high yield Composition (A).
Storage stability is poor sometimes for the organo-silicon compound being obtained by (pH is less than 7) hydrolytie polycondensation under acid condition.
In addition, in neutral conditions (near pH7), being sometimes difficult to hydrolysis condensation reaction.
In above-mentioned 1st operation, the condensation rate of compound (a1) and compound (a2) can be more than 92%, more preferably More than 95%, further preferred more than 98%.Most preferably siloxanes key generates the substantially all contracting of group (containing hydrolization group) Close, the upper limit of the condensation rate in the 1st operation is usually 99.9%.
Conventionally, there is known the method manufacturing organo-silicon compound in acid condition, but the chemical combination as starting compound Both thing (a1) and compound (a2) are difficult to homogeneous reaction, easily generate gel.It is thus known that having trimethylalkyoxys iotalane Or hexamethyl disiloxane etc. only has 1 siloxanes key and generates the silicon compound (hereinafter referred to as " M monomer ") of group and is used as envelope The end method to avoid gelation for the agent.
But, due to and with M monomer more than ormal weight, even if being avoided that gelation, the organo-silicon compound that obtain Inorganic in nature also has the tendency of decline.
On the other hand, according to manufacture method in the basic conditions, compound (a1) and compound (a2) can not made Carry out polycondensation in the case of there is gelation, and play the effect of the inorganic in nature that will not reduce gained solidfied material.
Composition (A) is to be to manufacture with above-mentioned 1st operation, and the manufacture method of composition (A) is acceptable as needed Including following operation.
The operation of the reactant liquor that (the 2nd operation) is obtained with acid neutralization the 1st operation.
The neutralizer that (the 3rd operation) obtains from the 2nd operation removes the operation of volatile ingredient.
(the 4th operation) makes concentrate that the 3rd operation obtains and the mixing of washing organic solvent and contact, is washing with organic The operation of at least solvent components (A) in solvent.
After (the 5th operation) washes the organic system liquid that the 4th operation obtains with water, obtain the organic solution containing composition (A) Operation.
The organic solution that (the 6th operation) obtains from the 5th operation removes the operation of volatile ingredient.
The manufacture method of composition (A) preferably comprises the 1st operation, the 2nd operation and the 5th operation.
In the manufacture of composition (A), the reactant liquor containing composition (A) after the reaction system, the 1st operation of the 1st operation, In organic system liquid and at least one of organic solution after the 5th operation after neutralizer after 2nd operation, the 4th operation, permissible Add the polymerization inhibitor stoping the polymerization of (methyl) acryloyl group.
When composition (A), (B) and (C) total is set to 100 weight portion, composition (A's) in the present composition contains Ratio is 5～50 weight portions, preferably 5～40 weight portions, more preferably 10～35 weight portions.
It is 5～50 weight portions by the content ratio that makes composition (A), can make and obtain hardness and excellent scratch resistance The compositionss of cured film.
2. composition (B)
The composition (B) of the present invention is by carabamate adducts (b1) (hereinafter referred to as " composition (b1) ") and (methyl) third (methyl) acrylate mixture that olefin(e) acid ester (b2) (hereinafter referred to as " composition (b2) ") is constituted, carabamate adducts (b1) Be by trivalent more than aliphatic polyol derived from, there are more than 2 (methyl) acryloyl groups and there is the (first of more than 1 hydroxyl Base) additive reaction of acrylate and polyisocyanates obtains, (methyl) acrylate (b2) be by trivalent more than aliphatic series many Derived from first alcohol, there are more than 3 (methyl) acryloyl groups and there is no (methyl) acrylate of hydroxyl.
The starting compound of composition (b1) be by trivalent more than aliphatic polyol derived from, there are more than 2 (methyl) third Enoyl- and there is (methyl) acrylate (hereinafter referred to as " hydroxyl multifunctional (methyl) acrylic acid of more than 1 hydroxyl Ester ").
As the aliphatic polyol more than trivalent of the starting compound of hydroxyl multifunctional (methyl) acrylate, can make Use various compounds, trimethylolpropane, tetramethylolmethane, double trimethylolpropane and dipentaerythritol etc. can be enumerated.
As hydroxyl multifunctional (methyl) acrylate, various compounds can be used, specifically can enumerate trihydroxy methyl third Alkane two (methyl) acrylate, two or three (methyl) acrylate of tetramethylolmethane, two or three (first of double trimethylolpropane Base) acrylate and dipentaerythritol two, three, four or five (methyl) acrylate etc..
Wherein, from the viewpoint of the hardness and excellent scratch resistance of cured film, preferably there are more than 3 (methyl) propylene Acyl group and have the compound of 1 hydroxyl, specifically can enumerate tetramethylolmethane three (methyl) acrylate, double trimethylolpropane three (methyl) acrylate and dipentaerythritol five (methyl) acrylate etc..
As the polyisocyanates of the opposing party's synthesis material of composition (b1), various compounds can be used.
As the example of preferred polyisocyanates, isophorone diisocyanate, hexa-methylene two Carbimide. can be enumerated Ester, 4,4 '-dicyclohexyl methyl hydride diisocyanate, norcamphane diisocyanate, 2,4 toluene diisocyanate and they Uric acid ester type trimer etc..
Composition (b1) is by the additive reaction synthesis of hydroxyl multifunctional (methyl) acrylate and polyisocyanates.This addition Reaction can be carried out under no catalyst, in order to effectively be reacted, can the stannum based compound such as dibutyl tin laurate and/ Or reacted in the presence of the catalyst such as the amine compound such as triethylamine.
Composition (b2) be by trivalent more than (methyl) acrylate derived from aliphatic polyol.
As the aliphatic polyol more than trivalent of the starting compound of composition (b2), can use with above-mentioned enumerate identical Alcohol.
As the concrete example of composition (b2), trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (first can be enumerated Base) acrylate, double trimethylolpropane four (methyl) acrylate and dipentaerythritol six (methyl) acrylate etc..
Wherein, from the viewpoint of the wearability and excellent scratch resistance of cured film, preferably there are more than 4 (methyl) third The compound of enoyl-, specifically can enumerate tetramethylolmethane four (methyl) acrylate, double trimethylolpropane four (methyl) propylene Acid esters and dipentaerythritol six (methyl) acrylate etc..
The composition (B) of the present invention is the mixture of composition (b1) and (b2).
The ratio of composition (b1) and (b2) suitably can set according to purpose.Mentioned component (B) preferably comprises (b1)：(b2)= 10：90～75：The mixture of 25 weight ratio, further preferably (b1)：(b2)=30：70～70：The mixing of 30 weight ratio Thing.
By the weight ratio that makes composition (b1) and (b2) within the range, can obtain forming hardness and marresistance is excellent The compositionss of different cured film.
With respect to total 100 weight portions of composition (A), (B) and (C), the composition (B) in the present composition containing than Example is 30～90 weight portions, preferably 40～90 weight portions, more preferably 50～85 weight portions.
It is 30～90 weight portions by the content ratio that makes composition (B), can be formed and can get hardness and marresistance is excellent The compositionss of different cured film.
3. composition (C)
The composition (C) of the present invention is that in addition to mentioned component (A) and mentioned component (B), intramolecular has nitrogen-atoms Free-radical polymerised unsaturated compound (hereinafter also referred to as " unsaturated compound (C) ").
By using above-mentioned unsaturated compound (C), the cured film that can get hardness and excellent scratch resistance can be formed Active energy ray-curable coating composition.In addition, in the case of containing aftermentioned specific compound (C1), can be formed viscous Spend substantially low compositionss, in the case of containing aftermentioned specific compound (C2), hardness and scratch resistance can not reduced Property in the case of improve cured film impact resistance.
In the present invention, the quantity of the free-radical polymerised unsaturated group that unsaturated compound (C) has is not special Limit, in the relatively low situation of the viscosity making compositionss, preferably there is the compound of 1 free-radical polymerised unsaturated group, that is, So-called simple function unsaturated compound.
As the concrete example of such simple function unsaturated compound, (methyl) acrylamide, N, N- dimethyl can be enumerated (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N- methylol (methyl) acrylamide, N- methoxy (methyl) acrylamide, N- butoxymethyl (methyl) acrylamide, N- isopropyl (methyl) acrylamide, N, N- dimethylamino The amide-containing lists such as base propylacrylamide, N- vinyl formamide, N- vinyl acetamide, two acetone (methyl) acrylamide Body；Dimethyl aminoethyl (methyl) acrylate, diethylamino ethyl (methyl) acrylate, t-butylamino ethyl The emulsion stabilities such as (methyl) acrylate；NVP；The lactams chemical combination such as N- vinyl-Epsilon-caprolactam Thing；The monomers containing morpholinyl such as (methyl) acryloyl morpholine；(methyl) acrylonitrile, N- N-cyclohexylmaleimide, N- phenyl horse Carry out acid imide etc..These compounds both can be used alone it is also possible to and use two or more.
Wherein, high from the Tg of the homopolymer, hardness of cured film that obtains and marresistance good from the viewpoint of, preferably contain Amide groups monomer, lactam compound and monomer containing morpholinyl (below, they are merged and be referred to as " compound (C1) ").As this Compound (C1), more preferably dimethyl (methyl) acrylamide, N- vinyl formamide, N- vinyl acetamide, (methyl) third Enoyl- morpholine.Wherein, the N- vinyl formamide as amide-containing monomer and N- vinyl acetamide, not only from above-mentioned solid The performance of compound and from reduce composition viscosity effect height from the viewpoint of, be preferred.
In addition, in unsaturated compound (C), intramolecular has the free-radical polymerised unsaturationization of isocyanuric acid system ring Compound (hereinafter referred to as " compound (C2) ") is individually or is preferred component with combining of compound (C1).As this compound (C2) two modified (methyl) acrylate of isocyanuric acid EO (oxirane), can be enumerated and isocyanuric acid EO (oxirane) changes Property three (methyl) acrylate and their mixture (as specific trade name, for example, East Asia synthesis society system " ア ロ ニ ッ Network ス M-313 " and " ア ロ ニ ッ Network ス M-315 ", Hitachi's chemical conversion society's system " Off ァ Application Network リ Le FA-731A ", Xin Zhong village Learn industrial society's system " NK ester A-9300 " etc.) etc. modified (methyl) esters of acrylic acid of alkylene oxide；Three modified [2- of 6-caprolactone (methyl) acryloyl-oxyethyl] (as specific trade name, for example, East Asia synthesizes society's system " ア ロ ニ ッ Network to chlorinated isocyanurates ス M-327 ", chemical industry society of Xin Zhong village system " NK ester A-9300-1CL " etc.) etc. modified (methyl) acrylate of 6-caprolactone Class；The trimer of hexamethylene diisocyanate and isophorone diisocyanate etc. 2 functional isocyanate and hydroxyl (first Base) acrylate etc. reactant (as specific trade name, industrial society's system " ア ト レ ジ Application UN-905 " for example, on root Deng), double (2- carbonyl ethyl) ester of isocyanuric acid 1,3- different with the carboxylate of (methyl) acrylic acid 2- hydroxy methacrylate, three (2- ethoxys) Three (methyl) acrylate of cyanurate, other isocyanuric acid derivatives (as specific trade name, are chemical conversion society of four countries " MA-DGIC ", " DA-MGIC ", " MeDAIC " of system, " AcDGIC " etc.).These compounds both can be used alone it is also possible to And use two or more.
As compound (C2), from the viewpoint of the impact resistance of the cured film obtaining is better, more preferably alkylene oxide Modified (methyl) esters of acrylic acid and (methyl) esters of acrylic acid of 6-caprolactone modification.
It is explained, the number of the free-radical polymerised unsaturated group that compound (C2) has is not particularly limited, Can be 1 or more than 2.In the present invention, from being readily obtained the cured film that hardness is high, marresistance is also good Viewpoint considers, preferably has the compound of more than 2 free-radical polymerised unsaturated groups.
When composition (A), (B) and (C) total is set to 100 weight portion, the unsaturated compound in the present composition (C) content ratio is 5～35 weight portions, preferably 5～30 weight portions, more preferably 8～25 weight portions.
By containing unsaturated compound (C) 5～35 weight portion, the solidification of hardness and excellent scratch resistance can be obtained Film.
In the present invention, in the case that unsaturated compound (C) is only made up of compound (C1), even if organic from not containing From the viewpoint of the viscosity of compositionss also can be reduced to coatable degree by solvent, by composition (A), (B) and the total of (C) set During for 100 weight portion, its content ratio is preferably 5～35 weight portions, more preferably 5～30 weight portions, further preferred 8～25 weights Amount part.
In the case that unsaturated compound (C) is only made up of compound (C2), more excellent anti-from obtaining having From the viewpoint of the cured film of impact, when composition (A), (B) and (C) total is set to 100 weight portion, its content ratio is excellent Elect 5～30 weight portions, more preferably 8～30 weight portions, further preferred 10～25 weight portions as.
And then, in the case that unsaturated compound (C) contains compound (C1) and (C2), from hardness, resistance to can be obtained From the viewpoint of the scratch resistance and all excellent cured film of impact resistance, the following institute of preferred content ratio of these compounds Show.When both total is set to 10～35 weight portion, content ratio preferably 5～30 weight portion of compound (C1), more preferably 5 ～25 weight portions, further preferred 8～25 weight portions, content ratio preferably 5～30 weight portion of compound (C2), more preferably 8 ～30 weight portions, further preferred 10～25 weight portions.By the content ratio of compound (C1) is set to 5～30 weight portions, Even if can obtain not using organic solvent also the viscosity of compositionss can be reduced to coatable degree, and hardness, scratch resistance Property and the excellent cured film of impact resistance.
4. active energy ray-curable coating composition
The active energy ray-curable coating composition of the present invention can make compositionss containing organic solvent and not Any one of compositionss containing organic solvent, different according to the species of composition (C), the combination containing organic solvent can be made Thing.For example, in the case that composition (C) contains compound (C1), the compositionss without organic solvent can be made.In addition, In the case of in the case that composition (C) contains compound (C2) or containing both compound (C1) and (C2), preferably comprise organic Solvent.Spendable organic solvent is as hereinafter described.
The compositionss of the present invention are necessary with composition (A), (B) and (C), according to purpose, photopolymerization can also be coordinated to cause The light stabilizers such as agent, pigment, dyestuff, surface conditioner, UV absorbent, HALS, in addition to composition (A), (B) and (C) Others have the various compositions such as compound and the organic polymer of free-radical polymerised unsaturated group.
Various compounds can be used as Photoepolymerizationinitiater initiater, as its concrete example, 2,2- dimethoxy -1,2- can be enumerated Diphenylethane -1- ketone, 1- hydroxy-cyclohexyl-phenyl ketone, 2- hydroxy-2-methyl -1- phenyl-propan -1- ketone, 1- [4- (2- Hydroxyl-oxethyl)-phenyl] -2- hydroxy-2-methyl -1- propane -1- ketone, 2- methyl isophthalic acid-[4- (methyl thio) phenyl] -2- Quinoline for propane -1- ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butane -1- ketone, diethoxy acetophenone, Oligomeric { 2- hydroxy-2-methyl -1- [4- (1- methyl ethylene) phenyl] acetone } and 2- hydroxyl -1- { 4- [4- (2- hydroxyl -2- first Base propionyl) benzyl] phenyl } the 1-Phenylethanone. based compound such as -2- methyl-propan -1- ketone；Benzophenone, 4- phenyl benzophenone, 2, The benzophenone based compound such as 4,6- tri-methyl benzophenone and 4- benzoyl -4 '-methyl-diphenyl sulfide；Toluyl Carbamate, 2- (2- oxo -2- phenylacetyl epoxide ethyoxyl) ethyl ester of phenyl acetic acid and the 2- of phenyl acetic acid The α -one ester based compound such as (2- hydroxyl-oxethyl) ethyl ester；2,4,6- trimethyl benzoyl diphenyl base phosphine oxide, double (2,4,6- Trimethylbenzoyl) oxygen such as phenyl phosphine oxide, double (2,6- Dimethoxybenzoyl) -2,4,4- trimethylpentylphosphine oxide Change phosphine based compound；Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether Deng benzoin based compound；Titanocenes based compound；1- [4- (4- benzoylphenyl sulfonyl) phenyl] -2- methyl -2- (4- Aminomethyl phenyl sulfinyl) 1-Phenylethanone ./benzophenone mixture photoinitiator such as propane -1- ketone；2- (O- benzoyl oximes)- The oxime ester system Photoepolymerizationinitiater initiaters such as 1- [4- (phenyl)] -1,2- acetyl caproyl；And camphorquinone etc..
When composition (A), (B) and (C) total is set to 100 weight portion, the preferred use level of Photoepolymerizationinitiater initiater is 0.1～10 weight portion, more preferably 0.5～7 weight portion, particularly preferred 1～5 weight portion.
It is 0.1～10 weight portion by the use level making Photoepolymerizationinitiater initiater, the curable of compositionss is excellent, can be made into energy Access the compositionss of the cured film of hardness and excellent scratch resistance.
Surface conditioner has the effect of levelability when improving the coating present composition and improves cured coating film Effect of soil resistance and flatness etc..As surface conditioner, preferably silicon-type surface conditioner or fluorine system surface conditioner. As concrete example, can enumerate and there is the silicon-type polymer of siloxane chain and polyalkylene oxide chain, there is perfluoroalkyl and polycyclic The fluorine system polymer of oxygen alkane chain and the fluorine system polymer with perfluoroalkyl ethers chain and polyalkylene oxide chain.
When composition (A), (B) and (C) total is set to 100 weight portion, the preferred use level of surface conditioner is 0.01～3 weight portion, more preferably 0.02～0.5 weight portion.By making use level be more than 0.01 weight portion, film can be improved Surface smoothness, suppression coating when bubble produce.
As long as the compound that others have free-radical polymerised unsaturated group is to have at least one in 1 molecule freely The compound of base polymerism unsaturated group, is just not particularly limited.
As the concrete example of the compound in 1 molecule with 1 free-radical polymerised unsaturated group, (methyl) can be enumerated Acrylic acid methyl ester., (methyl) ethyl acrylate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) third Olefin(e) acid cyclohexyl, (methyl) isobornyl acrylate, (methyl) acrylic acid dicyclopentenyl base ester, (methyl) acrylic acid bicyclopentyl Ester, (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) benzyl acrylate, styrene, (methyl) acrylic acid 2- hydroxypropyl acrylate, (methyl) Acrylic acid 4- hydroxy butyl ester, (methyl) acrylate of the alkylene oxide addition product of phenol the, (first of the alkylene oxide addition product of alkyl phenol Base) acrylate etc..
In addition, the compound in 1 molecule with more than 2 free-radical polymerised unsaturated groups is (hereinafter referred to as " other Multifunctional unsaturated compound ") adaptation to base material and hardness and marresistance can be improved.
Radical polymerization from the viewpoint of never reducing hardness and marresistance, in other multifunctional unsaturated compounds It is 3～20 in number preferably 1 molecule of conjunction property unsaturated group.
As other multifunctional unsaturated compounds, there is in preferably 1 molecule the change of more than 2 (methyl) acryloyl groups Compound.
As concrete example, two (methyl) acrylate, the Bisphenol F epoxy alkane addition of bisphenol-A epoxy alkane addition product can be enumerated Two (methyl) acrylate of thing, two (methyl) acrylate of bisphenol Z alkylene oxide addition product, bisphenol S alkylene oxide addition product Two (methyl) acrylate, two (methyl) acrylate of thiobisphenol alkylene oxide addition product, two (methyl) acrylic acid of bisphenol-A Ester, two (methyl) acrylate of Bisphenol F, two (methyl) acrylate of bisphenol Z, two (methyl) acrylate of bisphenol S, sulfur Two (methyl) acrylate for bis-phenol, tristane dihydroxymethyl two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) propylene Acid esters, Polyethylene Glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylic acid Ester, neopentyl glycol two (methyl) acrylate, 1,6-HD two (methyl) acrylate, 1,9- nonanediol two (methyl) propylene Acid esters, glycerol two (methyl) acrylate, two (methyl) acrylate of the alkylene oxide addition product of glycerol, dimeric dibasic acid glycol two (methyl) acrylate, cyclohexane dimethylol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, three Three (methyl) acrylate of the alkylene oxide addition product of hydroxymethyl-propane, three and tetraacrylate of tetramethylolmethane, tetramethylolmethane The three of alkylene oxide addition product and tetraacrylate, double trimethylolpropane four (methyl) acrylate, dipentaerythritol six-and Five-acrylate, polyester (methyl) acrylate, epoxy (methyl) acrylate, carbamate (methyl) acrylate, end End has organic siliconresin of (methyl) acryloyl group etc..
Wherein, as polyester (methyl) acrylate, PEPA and (methyl) acrylic acid dehydrating condensation can be enumerated Thing.As PEPA, can enumerate using ethylene glycol, Polyethylene Glycol, cyclohexane dimethylol, 3- methyl isophthalic acid, 5- pentanediol, The low molecular polylols such as propylene glycol, polypropylene glycol, 1,6-HD and trimethylolpropane or their alkylene oxide addition product Deng the binary acid such as polyol component and adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and p-phthalic acid or its Product and various dendrimeric polyols and (methyl) acrylic acid dehydration condensation etc. that the acid composition such as anhydride obtains.
As epoxy (methyl) acrylate, (methyl) acrylic acid adduct, the hydrogenation of bisphenol A type epoxy resin can be enumerated (methyl) propylene of (methyl) acrylic acid adduct, phenol or cresol novolak type epoxy resin of bisphenol A type epoxy resin The 2-glycidyl of the polyethers such as sour addition product, (methyl) acrylic acid adduct of biphenyl type epoxy resin, polytetramethylene glycol (methyl) acrylic acid adduct of base ether, (methyl) acrylic acid adduct of the diglycidyl ether of polybutadiene, polybutadiene (methyl) acrylic acid adduct of the internal epoxide of alkene, have epoxy radicals organic siliconresin (methyl) acrylic acid addition Thing, (methyl) acrylic acid adduct of limonene dioxide, 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylate (methyl) acrylic acid adduct etc..
As carbamate (methyl) acrylate, (methyl) third making organic multiple isocyanate and hydroxyl can be enumerated There is the additive reaction compound obtaining or (methyl) propylene making organic multiple isocyanate, polyhydric alcohol and hydroxyl in olefin(e) acid ester There is compound obtained from additive reaction in acid esters.
Here, as polyhydric alcohol, low molecular weight polyols, polyether polyol, PEPA, Merlon can be enumerated many First alcohol etc..
As low molecular weight polyols, ethylene glycol, propylene glycol, neopentyl glycol, hexamethylene two methylol, 3- first can be enumerated Base -1,5- pentanediol and glycerol etc..
As polyether polyol, polypropylene glycol or polytetramethylene glycol etc. can be enumerated.
As PEPA, can enumerate these low molecular weight polyols and/or polyether polyol and adipic acid, succinum The reactant of the acid composition such as the binary acid such as acid, phthalic acid, hexahydrophthalic acid and p-phthalic acid or its anhydride.
As organic multiple isocyanate, toluene di-isocyanate(TDI), XDI, durol can be enumerated Diformazan group diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 4,4 '-dicyclohexyl methyl hydride diisocyanate, six methylenes Group diisocyanate and isophorone diisocyanate etc..
As (methyl) acrylate of hydroxyl, (methyl) acrylic acid 2- hydroxyl ethyl ester, (methyl) acrylic acid 2- can be enumerated (methyl) acrylate of the hydroxyls of (methyl) hydroxyalkyl acrylates such as hydroxypropyl acrylate, (methyl) acrylic acid 4- hydroxy butyl ester Deng.
Organic polymer has the effect of warpage when reducing solidification while maintaining the transparency.Preferably organic polymer Thing is (methyl) acrylic polymer, as suitable composition monomer, can enumerate (methyl) acrylic acid methyl ester., (methyl) propylene Sour cyclohexyl, (methyl) acrylic acid, (methyl) glycidyl acrylate, N- (2- (methyl) acryloyl-oxyethyl) tetrahydrochysene are adjacent Phthalimide etc..In the case of the polymer making (methyl) acrylic acid copolymer, can be shunk with addition (methyl) acrylic acid Glyceride and in polymer chain introduce (methyl) acryloyl group.
Even if the compositionss of the present invention do not contain organic solvent sometimes, screening characteristics and operability are also excellent, but in order to more Improve these performances, or in order to adjust the viscosity of compositionss, it is possible to use organic solvent.As organic solvent, preferably can be molten The solvent of solution composition (A), (B) and (C).
As the concrete example of preferred organic solvent, the alcohol such as ethanol and isopropanol can be enumerated；Ethylene glycol single methyl ether and third The aklylene glycol monoether such as glycol monomethyl ether；The pyruvic alcohols such as DAA；The aromatic compounds such as toluene and dimethylbenzene；Propylene glycol The ester compounds such as monomethyl ether acetal, ethyl acetate, butyl acetate；The ketones such as acetone, butanone and methyl iso-butyl ketone (MIBK)；Two fourths The ethers such as base ether；N-Methyl pyrrolidone etc..
When composition (A), (B) and (C) total is set to 100 weight portion, the preferred use level of organic solvent is 10～ 1000 weight portions, more preferably 50～500 weight portions, further preferred 50～300 weight portions.
It is 10～1000 weight portions by the use level that makes organic solvent, can fully reduce the viscous of solidification compound Degree, therefore easily preparation adapt to known to coating process (excellent painting, roller coat, spin coating, dip-coating, intaglio plate coating, die head coating, flow coat, Spraying etc.) coating composition.
The viscosity (25 DEG C) being measured by E type viscometer of the active energy ray-curable coating composition of the present invention is from painting From the viewpoint of deposited property, preferably below 20,000mPa s, more preferably below 15,000mPa s, further preferred 10, Below 000mPa s.It is explained, lower limit is usually 100mPa s.
The manufacture method of the active energy ray-curable coating composition of the present invention according to conventional methods, can adopt Including the operation being stirred composition (A), composition (B), composition (C) and the other compositions using as needed and mix etc. Manufacture method.
5. coating method
The active energy ray-curable coating composition of the present invention is suitable to form the coated film high to the adaptation of base material.
The compositionss of the present invention are applicable to the base material being made up of various materials.As preferred base material, can enumerate timber, Metal, inorganic material and plastics etc..
As inorganic material, mortar, concrete and glass etc. can be enumerated.
As the concrete example of plastics, the acrylic resins such as polymethyl methacrylate, poly terephthalic acid second two can be enumerated The polyester resin such as alcohol ester, polrvinyl chloride, polycarbonate resin, epoxy resin and polyurethane resin etc..
The method compositionss of the present invention being coated on base material is not particularly limited, according to conventional methods.For example Excellent painting, roller coat, spin coating, dip-coating, intaglio plate coating, flow coat, spraying etc. can be applied.
In addition, as the specific method forming cured film, can enumerating after coating composition on base material, irradiate to film Method of activation-energy-ray etc..It is explained, as needed, before irradiating activation-energy-ray, can be through the drying process of film Or preheat operation.
Film and dried thickness suitably set according to purpose, in general, are 5～300 μm about.
As long as below the baking temperature or pre-heating temperature temperature the problems such as base material applied is not deformed, just not having There is particular determination.
As the activation-energy-ray being used for the curing of coating making to be made up of the present composition, electron ray, purple can be enumerated Outside line, luminous ray and X-ray etc., due to can use cheap device, preferably ultraviolet.
As ultraviolet lamp, high voltage mercury lamp, metal halide lamp, UV electrodeless lamp, LED etc. can be enumerated.
Irradiation energy as an example, can be enumerated and make according to the species of activation-energy-ray and the suitable setting of proportioning composition During with the situation of high voltage mercury lamp, preferably the irradiation energy in UV-A region is 100～5,000mJ/cm2, more preferably 200～1, 000mJ/cm2.
In the case of being solidified by electron ray, as spendable electron ray (EB) irradiation unit, can make Use various devices, for example, can enumerate, the dress of Cockcroft Walton type, Van de Graaff type and resonance transformer type Put, as electron ray, preferably apply the energy of 50～1000eV, more preferably 100～300eV.
The hardness of the cured film being obtained using the present composition and excellent scratch resistance.For example, based on JIS K 5600- The pencil hardness that 5-4 measures is usually more than 8H, can suppress the scratch causing because of the contact with metal parts etc..On having The material stating cured film can utilize its characteristic to be used for various uses.
The display of display panel used front panel, building materials purposes, ligthing paraphernalia, portable phone and smart mobile phone etc. for example can be enumerated The various prisms such as device or housing, the housing of family's electrical article, glasses.
As the concrete example of display panel used front panel, electric light telegraph board, display, billboard, advertisement and mark etc. can be enumerated.
As timber example as base material is used, the carpenter works such as stair, bed and furniture can be enumerated.As using metal As the example of base material, metallic articles such as kitchen panel for kitchen use and Stainless steel basin etc. can be enumerated.
Embodiment
Hereinafter, the present invention is illustrated based on embodiment.It is explained, the present invention is not limited to these embodiments.
In addition, " part " in following refers to " weight portion ", " % " refers to " weight % ".
1. the manufacture of composition (A)
Production Example 1 (manufacture of MAC-TQ)
1- propanol 150g and the tetramethoxy of alcohol exchange reaction is loaded in the reactor possess blender and thermometer Then they stirred, while being slowly added to 25% tetramethyl by silane (hereinafter referred to as " TMOS ") 36.53g (0.24mol) Methanolic ammonium hydroxide 4.37g (methanol 0.1mol, Tetramethylammonium hydroxide 12mmol), reacts 6 under 25 DEG C of temperature, pH9 Hour.Then, make internal temperature be 60 DEG C, stir and react 1 hour again.Here, reactant liquor gas chromatogram is divided Analysis (TCD detector) as a result, detect contain in TMOS 1～4 methoxyl group by positive propoxy 1 substituent replacing, 2 take Each compound for thing, 3 substituents or 4 substituents and unreacted TMOS.Only detect the TMOS of trace.In them containing just The ratio of propoxylated compounds (alkoxy silane containing positive propoxy) adds up to basic 100%.Based on the product in gas chromatogram The peak area of thing, obtains the replacement number (average of the positive propoxy in every 1 molecule compound containing positive propoxy) of 1- propanol, knot Fruit is 2.7.
Then, add 3- methacryloxypropyl trimethoxy silane 59.62g in above-mentioned reactant liquor (0.24mol), add water 30.2g.Then, add 25% Tetramethylammonium hydroxide-methanol solution 7.88g (methanol 0.18mol, Tetramethylammonium hydroxide 21.6mmol), stirring, while react 24 hours under 25 DEG C of temperature, pH9.Then, 10% aqueous solution of nitric acid 22.2g (35.3mmol) is added to be neutralized.Then, to the mixing of 120g Di Iso Propyl Ether and 180g water This neutralizer is added to be extracted in liquid.By washing this diisopropyl ether layer, remove salt and excessive acid, then, add N- nitrosophenylhydroxylamine aluminium salt " Q-1301 " (trade name) 11.5mg as the Wako Pure Chemical Industries, Ltd. of polymerization inhibitor.From To diisopropyl ethereal solution in, organic solvent is distilled off under reduced pressure, obtains water white solid organosilicon compound (hereinafter referred to as " MAC-TQ ").Its receipts amount is 57.72g.
With1H-NMR analyzes MAC-TQ, and results verification is by the 3- methacryloxypropyl three as compound (a1) Methoxy silane and the alkoxy silane containing positive propoxy as compound (a2) stoichiometrically react obtained from polycondensation Thing.
By MAC-TQ's1The content ratio of the alkoxyl (positive propoxy with silicon atom bonding) that H-NMR figure calculates, phase For the alkoxyl total amount containing in raw material, be equivalent to 2.5% amount.
In addition, the mean molecule quantity of MAC-TQ is measured as a result, pressing polystyrene standard by gel permeation chromatography (GPC) The Mn of conversion is 9600.
2. the manufacture of composition (B)
Production Example 2 (manufacture of HDI-M305)
To possess agitating device and 0.5L separating bottle that air is blown into pipe in be loaded as pentaerythritol triacrylate (with Lower referred to as " PETri ") and tetramethylol methane tetraacrylate (hereinafter referred to as " PETet ") mixture (containing PETri0.3mol with PETet0.2mol), East Asia synthesize society " ア ロ ニ ッ Network ス M-305 " (trade name, hereinafter referred to as " M-305 ") 159.2g, 2,6 di tert butyl 4 methyl phenol (hereinafter referred to as " BHT ") 0.092g and dibutyl tin laurate are (hereinafter referred to as For " DBTL ") 0.055g, liquid temperature is set as 70～75 DEG C, then they is stirred, while it is different to instill hexa-methylene two Cyanate (hereinafter referred to as " HDI ") 25.2g (0.15mol) is so as to react.
After the instillation of HDI terminates, internal temperature is set to 80 DEG C, is further continued for reacting, stirs 3 hours.Subsequently, by reaction The IR (INFRARED ABSORPTION) of product is analyzed to identify NCO and disappears, terminating reaction.Hereinafter, this product is referred to as " HDI- M305”.
HDI-M305 be containing as PETri and the product of HDI carabamate adducts (b1) and not with HDI The PETet (being equivalent to compound (b2)) of reaction, and their weight ratio (b1)：(b2)=6：4 mixture.
3. the manufacture of active energy ray-curable coating composition and evaluation
Using the composition shown in MAC-TQ and HDI-M305 obtained above and table 1, manufacture active energy ray-curable and apply Feed composition, for various evaluations.
Table 1
Embodiment 1-1～embodiment 1-4 and comparative example 1-1～1-4
Use each raw material in the ratio shown in table 2, according to conventional methods, stirring at normal temperatures, mixing, prepare activation energy and penetrate Line curable coating composition.
Then, measure 25 DEG C of each compositionss obtaining of viscosity by E type viscometer, the value obtaining is remembered in the lump in each In table.
Then, by each compositionss lowering the polyethylene terephthalate film in 7cm × 15cm × 50 μm side table Face, cover thereon be made up of polyethylene terephthalate and 50 μm of the thickness of transmitting UV mold release film.Then, lead to Crossing laminate layer roller and making the thickness after solidification is about 50 μm, the thickness of adjustment film.Another in polyethylene terephthalate film Face is also adopted by same method and forms film.Then, across mold release film, carry out ultraviolet irradiation under the following conditions, poly- to benzene The two sides of naphthalate film makes cured film.
Ultraviolet irradiates the ultraviolet irradiation machine (high voltage mercury lamp) using ア イ グ ラ Off ィ ッ Network ス society, with lamp height 19cm, line speed 2.3m/ minute, irradiate in one side unipath.The irradiation energy of every path passes through the photometer of EIT society " UV POWER PUCK " measures as a result, the irradiation energy in UV-A region is 900mJ/cm2.In addition, in UV-A region, peak illumination For 170mW/cm2.
To the cured film obtaining, evaluate pencil hardness, marresistance and adaptation by method shown below.They comment Valency result is shown in table 2.
(1) pencil hardness
Pencil hardness is measured based on JIS K 5600-5-4.
(2) marresistance
On the surface of cured film, in the shape of the steel wool " ボ Application ス タ #0000 " of the Japanese steelwool company system of configuration Under state, apply 1200g/4cm2Load, calculate cut number during double rubs 400 times.Using this cut number, based on following bases Quasi- evaluation marresistance.Here,
" A " or " B " will be evaluated, and to be set to marresistance good.
A：There is no cut completely.
B：There is 1～9 cut.
C：There is the cut of more than 10.
[table 2]
Although each compositionss of embodiment 1～5 employ organic solvent, show 10850mPa s or it is following Viscosity, viscosity is sufficiently reduced to coatable degree.In addition confirm, its cured film shows that the good pencil of 8H～10H is hard Degree, excellent in abrasion resistance, marresistance is also excellent.Wherein, N- vinyl formamide (NVF) is used as the embodiment 3 of composition (C) ～5, the viscosity of compositionss is further reduced, and is conducive to screening characteristics during various coating.
In contrast to this, due to the composition (C) without the present invention, the viscosity of compositionss is very high, is for comparative example 1 34400mPa s, needs the necessity being diluted by organic solvent etc. high when operating and when applying.In addition, using The not unsaturated compound 1 of nitrogen atom, as a result, the lead of cured film in the comparative example 2 of 6- hexanediyl ester (HDDA) Hardness and marresistance all reduce.
Comparative example 3 and 4 is the content of present component (C) present invention provide that the experimental example of situation outside scope.? It is impossible to fully reduce the viscosity of compositionss in the very few comparative example 3 of the content of composition (C), conversely, the content mistake in composition (C) In many comparative examples 4, the pencil hardness of cured film and marresistance are low.
Embodiment 6～11 and comparative example 5
Each raw material uses each raw material shown in table 3, with the ratio shown in table 3, conventionally, stir at normal temperatures, Mixing, prepares active energy ray-curable coating composition.It is explained, the compositionss of the compositionss of comparative example 5 and comparative example 1 Identical.Measure the viscosity of each compositionss, according to the benchmark distinguished by described below, measure coating adaptive.Its result remember in the lump in Table 3.
A：Viscosity is below 100mPa s above 10,000mPa s
B：Viscosity is more than 10,000mPa s and in below 15,000mPa s
C：Viscosity is more than 15,000mPa s and in below 20,000mPa s
D：Viscosity is more than 20,000mPa s
Then, operate similarly to Example 1, form cured film on the two sides of polyethylene terephthalate film.Subsequently, In addition to above-mentioned (1) hardness and (2) marresistance, carry out the evaluation of following (3) impact resistance.These evaluation results are shown in Table 3.
(3) impact resistance (falling ball impact test)
The height of the surface 10cm of self-curing film falls the 25g iron ball based on JIS B 1501.Do not produce in cured film and draw When trace and crackle, the height rising 5cm every time repeats to fall the operation of iron ball, and record will not produce the height of cut and crackle Peak.This test is carried out to 5 solidfied materials, is evaluated by the meansigma methodss calculating the peak not producing cut and crackle anti- Impact.
It is explained, test is implemented under the conditions of 23 DEG C and 50%RH of constant temperature and humidity.
[table 3]
In addition, the viscosity of each compositionss of embodiment 6～11 is also sufficiently reduced to coatable degree.And then confirm, obtain To cured film all show that the good pencil hardness of 8H～10H, marresistance and impact resistance (falling ball impact test) are also excellent. Use the embodiment 9～11 of 2 kinds containing NVF especially as composition (C), the viscosity of compositionss is low, coating operation is easy.
On the other hand, comparative example 5 is the experimental example of the compositionss without present component (C), and its viscosity is high, and obtain consolidates Although hardness and the marresistance of changing film are excellent, the value of falling ball impact test is low, is 15cm, and impact resistance is poor.
Industrial applicability
It is each that the active energy ray-curable coating composition of the present invention is applied to timber, metal, inorganic material and plastics etc. Plant the coating of base material.

Claims (9)

1. active energy ray-curable coating composition, it contains：
(A) organo-silicon compound, the silicon compound (a1) containing (methyl) acryloyl group being represented by following formulas (1) and following logical The silicon compound (a2) that formula (2) represents press with respect to the above-mentioned silicon compound of above-mentioned silicon compound (a1) 1mol (a2) 0.3～ The ratio hydrolytie polycondensation of 1.8mol and obtain,
In formula (1), R1For the alkyl of carbon number 1～6, the aralkyl of carbon number 7～10 or carbon number 6～10, there is the organic of aryl Group, R2For the divalent saturated hydrocarbyl of carbon number 1～6, R3For hydrogen atom or methyl, X is hydrolization group, and multiple X can be mutually the same Or different, n is 0 or 1,
SiY4···(2)
In formula (2), Y generates group for siloxanes key, and multiple Y can be same to each other or different to each other；
(B) (methyl) acrylate mixture, it is made up of carabamate adducts (b1) and (methyl) acrylate (b2), Carabamate adducts (b1) be by trivalent more than aliphatic polyol derived from, have more than 2 (methyl) acryloyl groups and The additive reaction of (methyl) acrylate and polyisocyanates with more than 1 hydroxyl obtains, (methyl) acrylate (b2) be by trivalent more than aliphatic polyol derived from, there are more than 3 (methyl) acryloyl groups and there is no the (first of hydroxyl Base) acrylate,
And
(C) intramolecular in addition to mentioned component (A) and mentioned component (B) has the free-radical polymerised unsaturationization of nitrogen-atoms Compound,
The content of mentioned component (A), mentioned component (B) and mentioned component (C) with them when adding up to 100 weight portion, on Stating composition (A) is 5～50 weight portions, and mentioned component (B) is 30～90 weight portions, and mentioned component (C) is 5～35 weight portions.
2. the active energy ray-curable coating composition described in claim 1, wherein, above-claimed cpd (a1) is formula (1) In X be the compound that alkoxyl and n are 0, above-claimed cpd (a2) is the compound that Y in formula (2) is alkoxyl.
3. the active energy ray-curable coating composition described in claim 1 or 2, wherein, mentioned component (C) contains to be selected from and contains At least one compound (C1) of morpholinyl monomer, amide-containing monomer and lactam compound.
4. the active energy ray-curable coating composition described in claim 3, wherein, above-claimed cpd (C1) is selected from propylene Acyl group morpholine, at least one of N- vinyl formamide, N- vinyl acetamide and N- vinyl-Epsilon-caprolactam.
5. the active energy ray-curable coating composition described in claim 4, wherein, above-claimed cpd (C1) at least contains N- Vinyl formamide.
6. the active energy ray-curable coating composition described in claim 1 or 2, wherein, mentioned component (C) is different containing having The compound (C2) of cyanuric acid system ring, the content of this compound (C2) is 5～30 weight portions.
7. the active energy ray-curable coating composition described in claim 6, wherein, above-claimed cpd (C2) is by alkylene oxide Or the free-radical polymerised unsaturated compound of caprolactone modification.
8. the active energy ray-curable coating composition described in claim 1 or 2, wherein, by mentioned component (A), above-mentioned one-tenth When point (B) and mentioned component (C) total is set to 100 weight portion, the content of mentioned component (C) is 10～35 weight portions,
Mentioned component (C) contains at least one compound selected from monomer containing morpholinyl, amide-containing monomer and lactam compound (C1) when and there is the compound (C2) of isocyanuric acid system ring, both total being set to 10～35 weight portion, above-claimed cpd (C1) content ratio is 5～30 weight portions, and the content ratio of above-claimed cpd (C2) is 5～30 weight portions.
9. cured film is it is characterised in that active energy ray-curable coating composition described in any one of claim 1～8 Obtain.
CN201480007642.2A 2013-03-26 2014-03-24 active energy ray-curable coating composition Active CN104981525B (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
JP2013-063132 2013-03-26
JP2013063132 2013-03-26
JP2013-077486 2013-04-03
JP2013077486 2013-04-03
PCT/JP2014/058050 WO2014157070A1 (en) 2013-03-26 2014-03-24 Active-energy-ray-curable coating composition

Publications (2)

Publication Number Publication Date
CN104981525A CN104981525A (en) 2015-10-14
CN104981525B true CN104981525B (en) 2017-03-08

Family

ID=51624044

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480007642.2A Active CN104981525B (en) 2013-03-26 2014-03-24 active energy ray-curable coating composition

Country Status (5)

Country Link
JP (1) JP6075443B2 (en)
KR (1) KR102158660B1 (en)
CN (1) CN104981525B (en)
TW (1) TWI617630B (en)
WO (1) WO2014157070A1 (en)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6186032B1 (en) * 2016-03-31 2017-08-23 ハリマ化成株式会社 Coating agent and coating film
JP6965186B2 (en) * 2017-03-13 2021-11-10 三洋化成工業株式会社 Photocurable resin composition
CN109369880A (en) * 2018-10-08 2019-02-22 武汉大学 A kind of photo curable aminomethyl phenyl organic silicon modified polyurethane (methyl) acrylate and its preparation method and application
US20230042417A1 (en) * 2019-12-31 2023-02-09 Dow Silicones Corporation Method of preparing silicone-acrylate hybrid composition and hybrid composition formed thereby

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102471642A (en) * 2009-07-28 2012-05-23 东亚合成株式会社 Actinic-energy-ray-curable adhesive composition for plastic film or sheet

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4348462A (en) 1980-07-11 1982-09-07 General Electric Company Abrasion resistant ultraviolet light curable hard coating compositions
JP3164407B2 (en) 1992-04-06 2001-05-08 三菱化学株式会社 Abrasion resistant UV curable coating composition
JP5443940B2 (en) * 2009-10-21 2014-03-19 東亞合成株式会社 Curable coating composition
JP5515609B2 (en) * 2009-10-21 2014-06-11 東亞合成株式会社 Photo-curable coating composition
JP5458797B2 (en) * 2009-10-21 2014-04-02 株式会社豊田自動織機 Vehicle member and manufacturing method thereof
WO2013035265A1 (en) * 2011-09-06 2013-03-14 株式会社豊田自動織機 Curable coating composition
JP5150759B1 (en) * 2011-09-06 2013-02-27 株式会社豊田自動織機 Curable coating composition

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102471642A (en) * 2009-07-28 2012-05-23 东亚合成株式会社 Actinic-energy-ray-curable adhesive composition for plastic film or sheet

Also Published As

Publication number Publication date
KR20150135243A (en) 2015-12-02
KR102158660B1 (en) 2020-09-22
TWI617630B (en) 2018-03-11
WO2014157070A1 (en) 2014-10-02
JP6075443B2 (en) 2017-02-08
CN104981525A (en) 2015-10-14
TW201443172A (en) 2014-11-16
JPWO2014157070A1 (en) 2017-02-16

Similar Documents

Publication Publication Date Title
Genest et al. The aza-Michael reaction as an alternative strategy to generate advanced silicon-based (macro) molecules and materials
TWI394801B (en) Uv-curable resin composition, uv-curable paint and coated article
CN104981525B (en) active energy ray-curable coating composition
CN102171265B (en) Curable resin composition and paint, and plastic molded product produced by laminating the same
US20130331600A1 (en) Michael Acceptor Having Multiple Hydroxyl Groups, and Michael Addition Product Derived Therefrom
CN1284982A (en) Liquid curable resin composition, coating, and cured coating therefrom
CN106459329A (en) Curable composition
CN1835981A (en) Photocrosslinkable polyurethanes
JPWO2009054508A1 (en) Curable composition containing a condensate of alkoxysilane
US6433097B1 (en) Curable polymer compositions and their preparation
CN107778485A (en) Polyesteramide acid and the photosensitive composite containing it
CN1557889A (en) Water wall paint for external wall
CN110191889A (en) Silsesquioxane derivative, its composition and low cure shrinkage cured film with free-radical polymerised functional group
TW201610028A (en) Active-energy-ray-curable composition
KR101543894B1 (en) UV curable top coating resin composition for coil-coating, the method for preparing the same and coil-coated steel sheet having a coating layer formed thereof
CN110551288B (en) Room-temperature self-repairing material and preparation method thereof
CN109071738A (en) Radically curing resin combination and its solidfied material
TW201428056A (en) Active energy ray-curable composition, cured coating film of same, and article having said cured coating film
CN107722685A (en) Thermosetting composition, cured film and colored filter
CN111377817A (en) Resin and ink
US5242955A (en) Composition comprising polyether compounds, a process for the preparation thereof and a curable resin composition
JP6465724B2 (en) Polyamide resin and polyimide resin
JP2002167426A (en) Curable resin composition, clear coating material composition, and method for coating
CN108628097A (en) Photosensitive composite, cured film, colored filter, display element, solid-state imager and LED illuminant heart
JP4320952B2 (en) Curable composition

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant