CN104981525A - Active-energy-ray-curable coating composition - Google Patents

Active-energy-ray-curable coating composition Download PDF

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CN104981525A
CN104981525A CN201480007642.2A CN201480007642A CN104981525A CN 104981525 A CN104981525 A CN 104981525A CN 201480007642 A CN201480007642 A CN 201480007642A CN 104981525 A CN104981525 A CN 104981525A
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methyl
compound
acrylate
composition
mentioned component
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CN104981525B (en
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小仓绢子
北村昭宪
古田尚正
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Toagosei Co Ltd
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Toagosei Co Ltd
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    • 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

Abstract

An active-energy-ray-curable coating composition according to the invention of the present application comprises the following components (A) to (C) at a specified content ratio: (A) an organosilicon compound produced by the hydrolysis and copolycondensation of a (meth)acryloyl-group-containing silicon compound (a1) represented by general formula (1) and a silicon compound (a2) represented by the formula SiY4 (wherein Y represents a group capable of generating a siloxane bond) at the ratio of 0.3 to 1.8 moles of the component (a2) per 1 mole of the component (a1); (B) a (meth)acrylate mixture composed of a urethane adduct compound (b1) and a (meth)acrylate (b2), wherein the component (b1) is produced by the addition reaction of a (meth)acrylate that is derived from an aliphatic polyhydric alcohol having a valency of 3 or more and has at least two (meth)acryloyl groups and at least one hydroxy group with a polyisocyanate and the component (b2) has at least three (meth)acryloyl groups and has no hydroxy group; and (C) a radically polymerizable unsaturated compound having a nitrogen atom in the molecule.

Description

Active energy ray-curable coating composition
Technical field
The present invention relates to active energy ray-curable coating composition, belong to the technical field of active energy ray-curable composition and coating.
Background technology
In recent years, in the indicating meters such as touch-screen universal just rapidly or smart mobile phone, use glass, but the glass in order to lightweight and when preventing breakage disperses, and is studying instead of plastics.
In general, the quality of plastic basis material is light, the excellence such as shock resistance and easy plasticity, but surface easily scratches, and hardness is low, there is the shortcoming of significantly infringement outward appearance when therefore directly using.Therefore, usually use the surface of coating composition applied plastic base material, carry out so-called hard coat process, give wear resistance and scuff resistance etc.
For coating composition in the past, be use the coating composition being dissolved with resin in a solvent, be coated in dry after on base material and form resin molding, but in order to improve productivity etc., also studying Photocurable composition and heat-curable composition always.
At this, as the hard paint put on plastic basis material, propose the hard paint of ultra-violet solidified acrylic acid or the like, the hard paint of Thermocurable silicon-type etc.
Although the wear resistance of the hard paint of the silicon-type of Thermocurable and excellent scratch resistance, exist following problem: set time is long, productivity is poor, and sometimes produce substrate deformation etc. because needing high temperature during solidification.In contrast to this, the general wear resistance of the hard paint of ultra-violet solidified acrylic acid or the like and scuff resistance poor, but set time is short, productivity is excellent.
As mentioned above, the hard paint of ultra-violet solidified acrylic acid or the like is relative to heat-curable composition, from the viewpoint of productivity and energy-conservation be excellent, in order to play this speciality, carried out the wear resistance of cured film and the research of scuff resistance of the insufficient performance of raising.
Such as, there will be a known and coordinate colloid silica in the composition or coordinate the method with the silane compound of (methyl) acryloxy.
Particularly, there will be a known containing colloid silica, have the ultraviolet-curable coating composition (patent documentation 1) of the organoalkoxysilane of (methyl) acryloxy and acrylate, containing containing the ultraviolet-curable coating composition (patent documentation 2) in the organoalkoxysilane of isocyanic ester and molecule with the reactant of the polyfunctional acrylic ester of hydroxyl and more than 3 acryls, the polyfunctional acrylic ester with more than 3 acryls and colloid silica.
But these coating compositions are compared with ultraviolet-curable coating composition in the past, although the wear resistance of cured film and excellent scratch resistance, both wear resistance and scuff resistance can not be met simultaneously, or not there is the practical upper performance met.In addition, different according to used base material, adaptation is insufficient sometimes.
To this, as wear resistance, scuff resistance and the hard paint excellent with the adaptation of base material etc., applicant proposed the light solidified coating composition (patent documentation 3) containing specific silicoorganic compound.
Patent documentation 1: the clear 57-500984 publication of special public table
Patent documentation 2: JP 5-287215 publication
Patent documentation 3: JP 2011-88996 publication
Summary of the invention
The problem that invention will solve
But the light solidified coating composition described in patent documentation 3, in order to regulate the viscosity of composition, give coating adaptive, must adopt organic solvent.Therefore, such as, in the situation etc. of carrying out thick film coating, sometimes distillation removing solvent spend time, the leeway be improved.
In general, when replacing organic solvent complex reaction monomer etc. to adjust composition viscosity, due to hardness and the scuff resistance decline of cured article, the cured film obtained can not be fully satisfactory as hard coat.Therefore, seeking solvent-free system, meet hardness and scuff resistance, coating composition by the active energy ray curable such as electron rays, ultraviolet.
In addition, in general, by coordinating in molecule the unsaturated compound with long-chain segment in solidification compound, the Tg of cured article reduces, shock resistance improves.But such cured film declines due to cross-linking density, there is the tendency of hardness and scuff resistance decline.Therefore, hardness and scuff resistance is being sought to be met and the solidification compound of the also excellent cured film of shock resistance.
Problem of the present invention is to provide not containing the active energy ray-curable coating composition of organic solvent, the viscosity of this active energy ray-curable coating composition is fully reduced to the degree that can apply, when being applied to the base materials such as plastics, its cured film demonstrates sufficient hardness and scuff resistance.
In addition, problem of the present invention is to provide active energy ray-curable coating composition, and its viscosity is fully reduced to the degree that can apply, and when being applied to the base materials such as plastics, its cured film demonstrates sufficient hardness and scuff resistance, and shock resistance is also excellent.
Solve the means of problem
The present inventor etc. conduct in-depth research to solve above-mentioned problem, found that, by using the composition containing the compound with nitrogen-atoms and free-radical polymerised unsaturated group, even if with an organic solvent also composition can be adjusted to the viscosity that can fully apply, the cured article of hardness and excellent scratch resistance can be obtained.In addition, the discoveries such as the present inventor, by using the composition of compound containing having tricarbimide system ring (イ ソ シ ア ヌ ル Ring) and free-radical polymerised unsaturated group, can obtain that hardness is high, the cured film of scuff resistance and shock resistance also excellence, so far completing the present invention.
The present invention is as described below.
[1] active energy ray-curable coating composition, contains:
(A) silicoorganic compound; it is obtained according to the ratio being 0.3 ~ 1.8 mole relative to above-mentioned silicon compound (a1) 1 mole of above-mentioned silicon compound (a2) polycondensation that is hydrolyzed by the silicon compound (a2) represented containing silicon compound (a1) and the following general formula (2) of (methyl) acryl that makes following general formula (1) represent
[changing 1]
(in general formula (1), R 1for the organic group with aryl of the alkyl of carbon number 1 ~ 6, the aralkyl of carbon number 7 ~ 10 or carbon number 6 ~ 10, R 2for the divalent saturated hydrocarbyl of carbon number 1 ~ 6, R 3for hydrogen atom or methyl, X is hydrolization group, and multiple X can be same to each other or different to each other, and n is 0 or 1)
SiY 4···(2)
(in general formula (2), Y is that siloxane bond generates group, 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 3 valencys more than aliphatic polyol derivative, there are more than 2 (methyl) acryls and the addition reaction of (methyl) acrylate and polyisocyanates with more than 1 hydroxyl obtains, (methyl) acrylate (b2) be by 3 valencys more than aliphatic polyol derivative, there are more than 3 (methyl) acryls and not there is (methyl) acrylate of hydroxyl,
And
(C) the free-radical polymerised unsaturated compound except mentioned component (A) and mentioned component (B), there is in molecule nitrogen-atoms,
The content of mentioned component (A), mentioned component (B) and mentioned component (C) with they add up to 100 weight part time, mentioned component (A) is 5 ~ 50 weight parts, mentioned component (B) is 30 ~ 90 weight parts, mentioned component (C) is 5 ~ 35 weight parts.
[2] active energy ray-curable coating composition described in above-mentioned [1], wherein, above-claimed cpd (a1) is that the X in general formula (1) is alkoxyl group and n is the compound of 0,
Above-claimed cpd (a2) is the Y in general formula (2) is the compound of alkoxyl group.
[3] above-mentioned [1] or the active energy ray-curable coating composition described in [2], wherein, mentioned component (C) is containing at least a kind of compound (C1) be selected from containing morpholinyl monomer, amide-containing monomer and lactam compound.
[4] active energy ray-curable coating composition described in above-mentioned [3]; wherein, above-claimed cpd (C1) is for being selected from acryloyl morpholine, N-vinyl formamide, N-vinyl acetamide and N-vinyl-Epsilon-caprolactam at least a kind.
[5] active energy ray-curable coating composition described in any one of above-mentioned [1] ~ [4], wherein, mentioned component (C) is containing the compound (C2) with tricarbimide system ring, and the content of this compound (C2) is 5 ~ 30 weight parts.
[6] active energy ray-curable coating composition described in above-mentioned [5], wherein, above-claimed cpd (C2) is the free-radical polymerised unsaturated compound by oxirane or caprolactone modification.
[7] active energy ray-curable coating composition described in any one of above-mentioned [1] ~ [6], wherein, by mentioned component (A), when the total of mentioned component (B) and mentioned component (C) is set to 100 weight part, the content of mentioned component (C) is 10 ~ 35 weight parts, mentioned component (C) is containing being selected from containing morpholinyl monomer, at least a kind of compound (C1) of amide-containing monomer and lactam compound and there is the compound (C2) of tricarbimide system ring, when both totals are set to 10 ~ 35 weight part, above-claimed cpd (C1) containing proportional be 5 ~ 30 weight parts, above-claimed cpd (C2) containing proportional be 5 ~ 30 weight parts.
Invention effect
The composition of an embodiment of the present invention can be made not containing the composition of organic solvent, can be formed and have the also excellent cured film of high hardness, scuff resistance relative to the various base materials such as plastics.
In addition, according to the composition of other embodiments of the present invention, can be formed, relative to the various base materials such as plastics, there is the also excellent cured film of high hardness, scuff resistance and shock resistance.
Embodiment
Active energy ray-curable coating composition of the present invention contains mentioned component (A), (B) and (C), relative to their total 100 weight part,
(A) composition 5 ~ 50 weight part,
(B) composition 30 ~ 90 weight part, and
(C) composition 5 ~ 35 weight part.
Below, each composition and composition is described in detail.
Be explained, in this specification sheets, acryl or methacryloyl be expressed as " (methyl) acryl ", acrylate or methacrylic ester be expressed as " (methyl) acrylate ".
1. composition (A)
Composition of the present invention (A) silicoorganic compound that to be the silicon compound (a2) (hereinafter referred to as " compound (a2) ") represented containing silicon compound (a1) (hereinafter referred to as " compound (a1) ") and the following general formula (2) of (methyl) acryl by making following general formula (1) represent obtain with the ratio hydrolytie polycondensation that is 0.3 ~ 1.8 mole relative to compound (a1) 1 mole compound (a2).
[changing 1]
(in general formula (1), R 1for the organic group with aryl of the alkyl of carbon number 1 ~ 6, the aralkyl of carbon number 7 ~ 10 or carbon number 6 ~ 10, R 2for the divalent saturated hydrocarbyl of carbon number 1 ~ 6, R 3for hydrogen atom or methyl, X is hydrolization group, and multiple X can be same to each other or different to each other, and n is 0 or 1)
SiY 4···(2)
(in general formula (2), Y is that siloxane bond generates group, and multiple Y can be same to each other or different to each other)
In the general formula (1) representing compound (a1), R 1for the organic group with aryl of the alkyl of carbon number 1 ~ 6, the aralkyl of carbon number 7 ~ 10 or carbon 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 composition obtained, more preferably methyl.
R 2for the divalent saturated hydrocarbyl of carbon number 1 ~ 6, preferred alkylidene group.As alkylidene group, from the viewpoint of excellent in abrasion resistance, the raw materials cost of the cured film of the composition obtained, more preferably trimethylene.R 3for 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 have water-disintegrable group, various group can be adopted.Specifically can enumerate hydrogen atom, alkoxyl group, cycloalkyloxy, aryloxy and alkoxy aryl.Wherein, preferred alkoxyl group, the more preferably alkoxyl group of carbon number 1 ~ 6.As the concrete example of alkoxyl group, methoxyl group, oxyethyl group, propoxy-, butoxy, pentyloxy and hexyloxy etc. can be enumerated.
In addition, n is 0 or 1, from the viewpoint of the excellent in abrasion resistance of the cured film of the composition obtained, is preferably 0.
In general formula (1), n as preferred compound is 0 and X is the concrete example of the compound of alkoxyl group, can enumerate 2-(methyl) acryloyl-oxyethyl triethoxyl silane, 3-(methyl) acryloxypropyl Trimethoxy silane and 3-(methyl) acryloxypropyl ethyl triethoxysilane etc.
In the general formula (2) representing compound (a2), Y is that siloxane bond generates group, and the multiple siloxane bonds in 1 molecule generate group and can be same to each other or different to each other.
Group is generated, preferred alkoxyl group as siloxane bond.As the preference of alkoxyl group, the alkoxyl group of the carbon numbers 1 ~ 4 such as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy and sec-butoxy can be enumerated.
The alkoxysilane compound containing trialkylsilyl group in molecular structure that the preferred concrete example of compound (a2) is four positive propoxy silane, trimethoxy-positive propoxy silane, dimethoxy two-positive propoxy silane, methoxyl group three-positive propoxy silane etc. have positive propoxy.
Alkoxysilane compound containing trialkylsilyl group in molecular structure containing positive propoxy both can be a kind of compound, also can be the mixture having positive propoxy, have the compound of other alkoxyl groups.
Mixture containing the alkoxysilane compound containing trialkylsilyl group in molecular structure of positive propoxy both can Multiple components used in combination, also directly can use and exchange by alcohol the compound manufactured.Such as, can alcohol permutoid reaction be there is by making in 1-propyl alcohol that above-mentioned general formula (2) represents and the silicon compound (such as, tetramethoxy-silicane) without positive propoxy and obtain.In addition, also the reaction product be obtained by reacting by this can directly be used.
Composition (A) is by obtaining compound (a1) and compound (a2) with the ratio that is 0.3 ~ 1.8 mole relative to compound (a1) 1 mole compound (a2) the polycondensation (hereinafter referred to as " the 1st operation ") that is hydrolyzed.Be explained, the reaction conditions of hydrolytie polycondensation is not particularly limited, preferred alkaline condition, below, the 1st operation under alkaline condition is described.
About the reaction ratio of compound (a1) with compound (a2), relative to compound (a1) 1 mole, the ratio of compound (a2) is 0.3 ~ 1.8 mole, the ratio of preferred compound (a2) is 0.8 ~ 1.6 mole, and more preferably the ratio of compound (a2) is 1 ~ 1.4 mole.By reacting with this ratio, can effectively manufacture composition (A) when gelation after the neutralization reaction that do not react.
By carrying out above-mentioned 1st operation in the basic conditions, reacted gelation can be prevented, composition (A) can be manufactured with high yield.
Alkaline condition is specially, the pH of reaction system be greater than 7 value, preferred pH is more than 8, and more preferably pH is more than 9.Be explained, the upper limit is generally pH13.By making reaction system be above-mentioned pH, the composition (A) of excellent storage stability can be manufactured with high yield.
Storage stability is poor sometimes for the silicoorganic compound obtained by (pH is less than 7) hydrolytie polycondensation under acidic conditions.
In addition, in neutral conditions (near pH7), sometimes the polycondensation that is hydrolyzed is difficult to.
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 preferably more than 98%.Most preferably siloxane bond generates group (containing hydrolization group) all condensations substantially, and the upper limit of the condensation rate in the 1st operation is generally 99.9%.
Conventionally, there is known manufacture the method for silicoorganic compound in acid condition, but be difficult to homogeneous reaction as the compound (a1) of starting compound with both compound (a2), easily generate gel.Therefore, there will be a known and trimethylalkyoxys iotalane or hexamethyldisiloxane etc. only had silicon compound (hereinafter referred to as " M monomer ") that 1 siloxane bond generates group as end-capping reagent to avoid the method for gelation.
But, due to and with M monomer more than specified amount, even if can avoid gelation, the inorganic in nature of the silicoorganic compound obtained also has the tendency of decline.
On the other hand, according to manufacture method in the basic conditions, polycondensation can be carried out when not making compound (a1), with compound (a2), gelation occur, and play the effect of the inorganic in nature that can not reduce gained cured article.
Composition (A) is to manufacture with above-mentioned 1st operation, and the manufacture method of composition (A) can also comprise following operation as required.
The operation of the reaction solution that (the 2nd operation) obtains by acid neutralization the 1st operation.
The operation of the neutralizer removing volatile component that (the 3rd operation) obtains from the 2nd operation.
The enriched material that (the 4th operation) makes the 3rd operation obtain mixes with washing organic solvent and contacts, the operation of at least solvent components (A) in washing organic solvent.
(the 5th operation) obtains the operation of the organic solution containing composition (A) after washing the organic system liquid that the 4th operation obtains with water.
The operation of the organic solution removing volatile component that (the 6th operation) obtains from the 5th operation.
The manufacture method of composition (A) is preferably containing the 1st operation, the 2nd operation and the 5th operation.
In the manufacture of composition (A); in the reaction solution containing composition (A) after the reaction system, the 1st operation of the 1st operation, neutralizer, the organic system liquid after the 4th operation and the organic solution after the 5th operation after the 2nd operation at least a kind, the stopper of prevention (methyl) acryl polymerization can be added.
When the total of composition (A), (B) and (C) is set to 100 weight part, composition (A) in the present composition containing proportional be 5 ~ 50 weight parts, be preferably 5 ~ 40 weight parts, be more preferably 10 ~ 35 weight parts.
By make composition (A) containing proportional be 5 ~ 50 weight parts, the composition of the cured film obtaining hardness and excellent scratch resistance can be made.
2. composition (B)
Composition of the present invention (B) forms (methyl) acrylate mixture by carabamate adducts (b1) (hereinafter referred to as " composition (b1) ") and (methyl) acrylate (b2) (hereinafter referred to as " composition (b2) "), carabamate adducts (b1) be by 3 valencys more than aliphatic polyol derivative, there are more than 2 (methyl) acryls and the addition reaction of (methyl) acrylate and polyisocyanates with more than 1 hydroxyl obtains, (methyl) acrylate (b2) be by 3 valencys more than aliphatic polyol derivative, there are more than 3 (methyl) acryls and not there is (methyl) acrylate of hydroxyl.
The starting compound of composition (b1) be by 3 valencys more than aliphatic polyol derivative, there are more than 2 (methyl) acryls and there is (methyl) acrylate (hereinafter referred to as " hydroxyl multifunctional (methyl) acrylate ") of more than 1 hydroxyl.
As aliphatic polyols more than 3 valencys of the starting compound of hydroxyl multifunctional (methyl) acrylate, various compound can be used, TriMethylolPropane(TMP), tetramethylolmethane, ditrimethylolpropane and Dipentaerythritol etc. can be enumerated.
As hydroxyl multifunctional (methyl) acrylate, various compound can be used, specifically can enumerate two, three, four or five (methyl) acrylate etc. of TriMethylolPropane(TMP) two (methyl) acrylate, two or three (methyl) acrylate of tetramethylolmethane, two or three (methyl) acrylate of ditrimethylolpropane and Dipentaerythritol.
Wherein, from the viewpoint of hardness and the excellent scratch resistance of cured film; preferably there are more than 3 (methyl) acryls and there is the compound of 1 hydroxyl, specifically can enumerate tetramethylolmethane three (methyl) acrylate, ditrimethylolpropane three (methyl) acrylate and Dipentaerythritol five (methyl) acrylate etc.
As the polyisocyanates of the opposing party's synthesis material of composition (b1), various compound can be used.
As the example of preferred polyisocyanates, isophorone diisocyanate, hexamethylene diisocyanate, 4 can be enumerated, 4 '-dicyclohexyl methane diisocyanate, norcamphane vulcabond, 2,4 toluene diisocyanate and their uric acid ester type tripolymer etc.
Composition (b1) is synthesized by the addition reaction of multifunctional (methyl) acrylate of hydroxyl and polyisocyanates.This addition reaction can be carried out under catalyst-free, in order to effectively react, can react under the existence of the catalyzer such as amine compound such as tin based compound and/or triethylamine such as dibutyl tin laurate.
Composition (b2) be by 3 valencys more than derivative (methyl) acrylate of aliphatic polyol.
As aliphatic polyols more than 3 valencys of the starting compound of composition (b2), can use and the above-mentioned identical alcohol enumerated.
As the concrete example of composition (b2), trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate and Dipentaerythritol six (methyl) acrylate etc. can be enumerated.
Wherein, from the viewpoint of wear resistance and the excellent scratch resistance of cured film; preferably there is the compound of more than 4 (methyl) acryls, specifically can enumerate tetramethylolmethane four (methyl) acrylate, ditrimethylolpropane four (methyl) acrylate and Dipentaerythritol six (methyl) acrylate etc.
Composition of the present invention (B) is the mixture of composition (b1) and (b2).
The ratio of composition (b1) and (b2) can according to the suitable setting of object.Mentioned component (B) is preferably containing (b1): the mixture of the weight ratio of (b2)=10:90 ~ 75:25, more preferably containing (b1): the mixture of the weight ratio of (b2)=30:70 ~ 70:30.
By making the weight ratio of composition (b1) and (b2) within the scope of this, the composition of the cured film that can form hardness and excellent scratch resistance can be obtained.
Relative to total 100 weight part of composition (A), (B) and (C), composition (B) in the present composition containing proportional be 30 ~ 90 weight parts, be preferably 40 ~ 90 weight parts, be more preferably 50 ~ 85 weight parts.
By make composition (B) containing proportional be 30 ~ 90 weight parts, the composition of the cured film that can obtain hardness and excellent scratch resistance can be formed.
3. composition (C)
Composition of the present invention (C) is except mentioned component (A) and mentioned component (B), to have nitrogen-atoms in molecule free-radical polymerised unsaturated compound (hereinafter also referred to as " unsaturated compound (C) ").
By using above-mentioned unsaturated compound (C), the active energy ray-curable coating composition of the cured film that can obtain hardness and excellent scratch resistance can be formed.In addition, when containing aftermentioned specific compound (C1), the composition that viscosity is fully low can being formed, when containing aftermentioned specific compound (C2), the shock resistance of cured film can be improved when not reducing hardness and scuff resistance.
In the present invention, the quantity of the free-radical polymerised unsaturated group that unsaturated compound (C) has is not particularly limited, make the situation that the viscosity of composition is lower, preferably there is the compound of 1 free-radical polymerised unsaturated group, be i.e. so-called simple function unsaturated compound.
As the concrete example of such simple function unsaturated compound, (methyl) acrylamide, N can be enumerated, N-dimethyl (methyl) acrylamide, N, the amide-containing monomers such as N-diethyl (methyl) acrylamide, N-methylol (methyl) acrylamide, N-methoxymethyl (methyl) acrylamide, N-butoxymethyl (methyl) acrylamide, N-sec.-propyl (methyl) acrylamide, N, N-dimethylaminopropylacryl acid amides, N-vinyl formamide, N-vinyl acetamide, two acetone (methyl) acrylamide; The emulsion stabilities such as dimethyl aminoethyl (methyl) acrylate, diethylamino ethyl (methyl) acrylate, t-butylamino ethyl (methyl) acrylate; NVP; The lactam compounds such as N-vinyl-Epsilon-caprolactam; (methyl) acryloyl morpholine etc. are containing morpholinyl monomer; (methyl) vinyl cyanide, N-N-cyclohexylmaleimide, N-phenylmaleimide etc.These compounds both can be used alone, and also two or more kinds may be used.
Wherein,, the hardness of cured film that obtains high from the viewpoint of the Tg of homopolymer and scuff resistance good, preferred amide-containing monomer, lactam compound and containing morpholinyl monomer (following, their to be merged and is called " compound (C1) ").As this compound (C1), more preferably dimethyl (methyl) acrylamide, N-vinyl formamide, N-vinyl acetamide, (methyl) acryloyl morpholine.Wherein, as N-vinyl formamide and the N-vinyl acetamide of amide-containing monomer, not only from the viewpoint of above-mentioned Solidified enzyme but also high from reducing the effect of composition viscosity, be preferred.
In addition, in unsaturated compound (C), the free-radical polymerised unsaturated compound (hereinafter referred to as " compound (C2) ") in molecule with tricarbimide system ring is separately or is preferred component with the combination of compound (C1).As this compound (C2), (methyl) esters of acrylic acid of two (methyl) acrylate of tricarbimide EO (oxyethane) modification and the oxirane modification such as three (methyl) acrylate of tricarbimide EO (oxyethane) modification and their mixture (as concrete trade(brand)name, such as, for East Asia synthesis society's system " ア ロ ニ ッ Network ス M-313 " and " ア ロ ニ ッ Network ス M-315 ", Hitachi change into society's system " Off ァ Application Network リ Le FA-731A ", chemical industry society of Xin Zhong village system " NK ester A-9300 " etc.) can be enumerated, (methyl) esters of acrylic acid of the 6-caprolactone modifications such as three [2-(methyl) acryloyl-oxyethyl] chlorinated isocyanurates (as concrete trade(brand)name, such as, being East Asia synthesis society's system " ア ロ ニ ッ Network ス M-327 ", chemical industry society of Xin Zhong village system " NK ester A-9300-1CL " etc.) of 6-caprolactone modification, hexamethylene diisocyanate and isophorone diisocyanate etc. 2 the reactant of tripolymer and hydroxyl (methyl) acrylate etc. of functional isocyanate (as concrete trade(brand)name, be such as industrial society “ ア ー ト レ ジ Application UN-905 on root " etc.), tricarbimide 1, the carboxylate of two (2-carbonyl ethyl) ester of 3-and (methyl) vinylformic acid 2-hydroxy methacrylate, three (methyl) acrylate of three (2-hydroxyethyl) chlorinated isocyanurates, other isocyanuric acid derivatives is (as concrete trade(brand)name, for four countries change into " MA-DGIC " of society, " DA-MGIC ", " MeDAIC ", " AcDGIC " etc.).These compounds both can be used alone, and also two or more kinds may be used.
As compound (C2), better from the viewpoint of the shock resistance of the cured film obtained, (methyl) esters of acrylic acid of more preferably oxirane modification and (methyl) esters of acrylic acid of 6-caprolactone modification.
Be explained, the number of the free-radical polymerised unsaturated group that compound (C2) has is not particularly limited, and can be 1, also can be more than 2.The viewpoint of the cured film that in the present invention, the hardness that is easy to get calmly is high, scuff resistance is also good considers preferably have the compound of more than 2 free-radical polymerised unsaturated groups.
When the total of composition (A), (B) and (C) is set to 100 weight part, unsaturated compound (C) in the present composition containing proportional be 5 ~ 35 weight parts, preferably 5 ~ 30 weight parts, more preferably 8 ~ 25 weight parts.
By containing unsaturated compound (C) 5 ~ 35 weight part, the cured film of hardness and excellent scratch resistance can be obtained.
In the present invention, when unsaturated compound (C) is only made up of compound (C1), even if from the viewpoint of also the viscosity drop of composition not being low to moderate the degree that can apply containing organic solvent, by composition (A), (B) and the total of (C) is set to 100 weight part time, it is preferably 5 ~ 35 weight parts, more preferably 5 ~ 30 weight parts, further preferred 8 ~ 25 weight parts containing proportional.
When unsaturated compound (C) is only made up of compound (C2), from the viewpoint of obtaining the cured film with more excellent shock resistance, when the total of composition (A), (B) and (C) is set to 100 weight part, it is preferably 5 ~ 30 weight parts, more preferably 8 ~ 30 weight parts, further preferred 10 ~ 25 weight parts containing proportional.
And then, when unsaturated compound (C) is containing compound (C1) and (C2), from the viewpoint of obtaining all excellent cured film of hardness, scuff resistance and shock resistance, preferably containing of these compounds is proportional as follows.When both totals are set to 10 ~ 35 weight part, compound (C1) containing proportional preferably 5 ~ 30 weight parts, more preferably 5 ~ 25 weight parts, further preferred 8 ~ 25 weight parts, compound (C2) containing proportional preferably 5 ~ 30 weight parts, more preferably 8 ~ 30 weight parts, further preferred 10 ~ 25 weight parts.By compound (C1) is set to 5 ~ 30 weight parts containing proportional, even if can obtain with an organic solvent also the viscosity drop of composition not being low to moderate the degree that can apply, and the cured film of hardness, scuff resistance and shock resistance excellence.
4. active energy ray-curable coating composition
Active energy ray-curable coating composition of the present invention can make composition containing organic solvent and not containing any one of the composition of organic solvent, different according to the kind of composition (C), can make the composition containing organic solvent.Such as, when composition (C) is containing compound (C1), can make not containing the composition of organic solvent.In addition, when composition (C) containing compound (C2) or containing compound (C1) and (C2) both when, preferably contain organic solvent.Spendable organic solvent as hereinafter described.
Composition of the present invention with composition (A), (B) and (C) for necessary, according to object, the photostabilizers such as Photoepolymerizationinitiater initiater, pigment, dyestuff, surface conditioner, UV light absorber, HALS, the various composition such as other the compound with free-radical polymerised unsaturated group and organic polymer except composition (A), (B) and (C) can also be coordinated.
Various compound can be used as Photoepolymerizationinitiater initiater, as its concrete example, can 2 be enumerated, 2-dimethoxy-1, 2-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-morpholino 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-hydroxy-2-methyl propionyl) benzyl] phenyl } the methyl phenyl ketone based compound such as-2-methyl-propan-1-ketone, the benzophenone based compounds such as benzophenone, 4-phenyl benzophenone, 2,4,6-tri-methyl benzophenones and 4-benzoyl-4 '-methyl-diphenyl sulfide, the α-one ester based compounds such as 2-(2-oxo-2-phenylacetyl oxygen base oxethyl) ethyl ester of methylbenzoyl formate, oxygen base phenylacetic acid and 2-(2-hydroxyl-oxethyl) ethyl ester of oxygen base phenylacetic acid, the phosphine oxide based compounds such as TMDPO, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, two (2,6-Dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, the bitter almond oil camphor based compounds such as bitter almond oil camphor, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether, two luxuriant titanium sub-group compounds, methyl phenyl ketone/benzophenone mixture the photoinitiators such as 1-[4-(4-benzoylphenyl alkylsulfonyl) phenyl]-2-methyl-2-(4-aminomethyl phenyl sulfinyl) propane-1-ketone, the oxime ester system Photoepolymerizationinitiater initiaters such as 2-(O-benzoyl oximes)-1-[4-(phenyl)]-1,2-acetyl caproyl, and camphorquinone etc.
When the total of composition (A), (B) and (C) is set to 100 weight part, the preferred use level of Photoepolymerizationinitiater initiater is 0.1 ~ 10 weight part, more preferably 0.5 ~ 7 weight part, particularly preferably 1 ~ 5 weight part.
By making the use level of Photoepolymerizationinitiater initiater be 0.1 ~ 10 weight part, the solidified nature of composition is excellent, can be made into the composition of the cured film that can obtain hardness and excellent scratch resistance.
Surface conditioner has the effect of levelling property when improving the coating present composition and improves the didirtresistance of cured coating film and the effect etc. of smoothness.As surface conditioner, preferred silicon-type surface conditioner or fluorine system surface conditioner.As concrete example, can enumerate there is siloxane chain and polyalkylene oxide chain silicon-type polymkeric substance, there is the fluorine based polymer of perfluoroalkyl and polyalkylene oxide chain and there is the fluorine based polymer of perfluoroalkyl ethers chain and polyalkylene oxide chain.
When the total of composition (A), (B) and (C) is set to 100 weight part, the preferred use level of surface conditioner is 0.01 ~ 3 weight part, more preferably 0.02 ~ 0.5 weight part.By making use level be more than 0.01 weight part, the surface smoothness of film can be improved, suppress bubble when being coated with to produce.
As long as other the compound with free-radical polymerised unsaturated group is the compound in 1 molecule with at least 1 free-radical polymerised unsaturated group, be just not particularly limited.
As the concrete example of compound in 1 molecule with 1 free-radical polymerised unsaturated group, (methyl) methyl acrylate can be enumerated, (methyl) ethyl propenoate, (methyl) butyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) vinylformic acid dicyclopentenyl ester, (methyl) vinylformic acid bicyclopentyl ester, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) benzyl acrylate, vinylbenzene, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester, (methyl) acrylate of the oxirane affixture of phenol, (methyl) acrylate etc. of the oxirane affixture of alkylphenol.
In addition, the compound (hereinafter referred to as " other multifunctional unsaturated compound ") in 1 molecule with more than 2 free-radical polymerised unsaturated groups can improve the adaptation of base material and hardness and scuff resistance.
The viewpoint never reducing hardness and scuff resistance is considered, the number of the free-radical polymerised unsaturated group in other multifunctional unsaturated compound is preferably 3 ~ 20 in 1 molecule.
As other multifunctional unsaturated compound, preferably there is in 1 molecule the compound of more than 2 (methyl) acryls.
As concrete example, two (methyl) acrylate of bisphenol-A epoxy alkane affixture can be enumerated, two (methyl) acrylate of Bisphenol F epoxy alkane affixture, two (methyl) acrylate of bisphenol Z oxirane affixture, two (methyl) acrylate of bisphenol S oxirane affixture, two (methyl) acrylate of thiobisphenol oxirane affixture, two (methyl) acrylate of dihydroxyphenyl propane, two (methyl) acrylate of Bisphenol F, two (methyl) acrylate of bisphenol Z, two (methyl) acrylate of bisphenol S, two (methyl) acrylate of thiobisphenol, tristane dihydroxymethyl two (methyl) acrylate, ethylene glycol bisthioglycolate (methyl) acrylate, polyoxyethylene glycol two (methyl) acrylate, propylene glycol two (methyl) acrylate, polypropylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, 1,9-nonanediol two (methyl) acrylate, glycerine two (methyl) acrylate, two (methyl) acrylate of the oxirane affixture of glycerine, dimeracid glycol two (methyl) acrylate, cyclohexane dimethylol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, three (methyl) acrylate of the oxirane affixture of TriMethylolPropane(TMP), three and tetraacrylate of tetramethylolmethane, three and tetraacrylate of tetramethylolmethane oxirane affixture, ditrimethylolpropane four (methyl) acrylate, Dipentaerythritol six-and five-acrylate, polyester (methyl) acrylate, epoxy (methyl) acrylate, carbamate (methyl) acrylate, the silicone resin etc. of end has (methyl) acryl.
Wherein, as polyester (methyl) acrylate, polyester polyol and (methyl) acrylic acid dehydration condensation can be enumerated.As polyester polyol, can enumerate and make spent glycol, polyoxyethylene glycol, cyclohexane dimethylol, 3-methyl isophthalic acid, the reaction product that the sour compositions such as the diprotic acid such as polyhydroxy reactant and hexanodioic acid, succsinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid or its acid anhydrides such as the low molecular polylols such as 5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexylene glycol and TriMethylolPropane(TMP) or their oxirane affixture obtain and various dendrimeric polyols and (methyl) acrylic acid dehydration condensation etc.
As epoxy (methyl) acrylate, (methyl) acrylic acid adduct of bisphenol A type epoxy resin can be enumerated, (methyl) acrylic acid adduct of bisphenol-A epoxy resin, (methyl) acrylic acid adduct of phenol or cresol novolak type epoxy resin, (methyl) acrylic acid adduct of biphenyl type epoxy resin, (methyl) acrylic acid adduct of the diglycidyl ether of the polyethers such as polytetramethylene glycol, (methyl) acrylic acid adduct of the diglycidyl ether of polyhutadiene, (methyl) acrylic acid adduct of polyhutadiene inner loop oxide compound, there is (methyl) acrylic acid adduct of the silicone resin of epoxy group(ing), (methyl) acrylic acid adduct of limonene dioxide, 3, 4-epoxycyclohexyl-methyl-3, (methyl) acrylic acid adduct etc. of 4-epoxycyclohexane carboxylate.
As carbamate (methyl) acrylate, the compound that (methyl) acrylate generation addition reaction of organic multiple isocyanate and hydroxyl is obtained or (methyl) acrylate generation addition reaction making organic multiple isocyanate, polyvalent alcohol and hydroxyl can be enumerated and the compound obtained.
At this, as polyvalent alcohol, low molecular weight polyols, polyether glycol, polyester polyol, polycarbonate polyol etc. can be enumerated.
As low molecular weight polyols, ethylene glycol, propylene glycol, neopentyl glycol, hexanaphthene two methylol, 3-methyl isophthalic acid can be enumerated, 5-pentanediol and glycerine etc.
As polyether glycol, polypropylene glycol or polytetramethylene glycol etc. can be enumerated.
As polyester polyol, the reactant by these low molecular weight polyols and/or the sour composition such as the diprotic acid such as polyether glycol and hexanodioic acid, succsinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid or its acid anhydrides can be enumerated.
As organic multiple isocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethyl-xylylene diisocyanate, 4 can be enumerated, 4 '-diphenylmethanediisocyanate, 4,4 '-dicyclohexyl methane diisocyanate, hexamethylene diisocyanate and isophorone diisocyanate etc.
As (methyl) acrylate of hydroxyl, (methyl) acrylate etc. of the hydroxyl of (methyl) hydroxyalkyl acrylates such as (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxy butyl ester can be enumerated.
Organic polymer has the effect reducing warpage when solidifying while maintaining the transparency.Preferred organic polymer is (methyl) acrylic polymers, as suitable formation monomer, (methyl) methyl acrylate, (methyl) cyclohexyl acrylate, (methyl) vinylformic acid, (methyl) glycidyl acrylate, N-(2-(methyl) acryloyl-oxyethyl) tetrahydric phthalimide etc. can be enumerated.When making the polymkeric substance of (methyl) acrylic acid copolymer, can addition (methyl) glycidyl acrylate and in polymer chain introduce (methyl) acryl.
Even if composition of the present invention is not sometimes containing organic solvent, screening characteristics and operability are also excellent, but in order to more improve these performances, or in order to adjust the viscosity of composition, can be with an organic solvent.As organic solvent, the preferably solvent of energy solvent components (A), (B) and (C).
As the concrete example of preferred organic solvent, the alcohol such as ethanol and Virahol can be enumerated; The aklylene glycol monoethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; The hydroxyacetones such as diacetone alcohol; The aromatic substance such as toluene and dimethylbenzene; The ester cpds such as propylene glycol monomethyl ether acetal, ethyl acetate, butylacetate; The ketones such as acetone, butanone and methyl iso-butyl ketone (MIBK); The ethers such as dibutyl ether; N-Methyl pyrrolidone etc.
When the total of composition (A), (B) and (C) is set to 100 weight part, the preferred use level of organic solvent is 10 ~ 1000 weight parts, more preferably 50 ~ 500 weight parts, further preferred 50 ~ 300 weight parts.
Be 10 ~ 1000 weight parts by making the use level of organic solvent, fully can reduce the viscosity of solidification compound, therefore easily preparation adapts to the coating composition of known coating process (rod painting, roller coat, spin coating, dip-coating, intaglio plate coating, die head coating, flow coat, spraying etc.).
Active energy ray-curable coating composition of the present invention by the viscosity (25 DEG C) of E type viscometer determining from the viewpoint of screening characteristics, preferably 20, below 000mPas, more preferably 15, below 000mPas, further preferably 10, below 000mPas.Be explained, lower limit is generally 100mPas.
The manufacture method of active energy ray-curable coating composition of the present invention according to conventional methods, can adopt the manufacture method comprising and composition (A), composition (B), composition (C) and other compositions of using as required are carried out the operation of Agitation and mixing etc.
5. coating method
Active energy ray-curable coating composition of the present invention is suitable for forming the coated film high to the adaptation of base material.
Composition of the present invention is applicable to the base material be made up of various material.As preferred base material, timber, metal, inorganic materials and plastics etc. can be enumerated.
As inorganic materials, mortar, concrete and glass etc. can be enumerated.
As the concrete example of plastics, the vibrin such as acrylic resin, polyethylene terephthalate, polyvinyl chloride, polycarbonate resin, epoxy resin and the urethane resins etc. such as polymethylmethacrylate can be enumerated.
The method that composition of the present invention is coated on base material is not particularly limited, according to conventional methods.Such as can apply rod painting, roller coat, spin coating, dip-coating, intaglio plate coating, flow coat, spraying etc.
In addition, as the concrete method forming cured film, can enumerate on base material after coating composition, irradiate the method etc. of activation-energy-ray to film.Be explained, as required, before irradiation activation-energy-ray, can be passed through the drying process of film or preheat operation.
Film and dried thickness set according to object is suitable, in general, are about 5 ~ 300 μm.
As long as drying temperature or pre-heating temperature do not produce below the temperature of the problems such as distortion at applied base material, be just not particularly limited.
As the activation-energy-ray for making the curing of coating be made up of the present composition, electron rays, ultraviolet, visible rays and X-ray etc. can be enumerated, due to cheap device can be used, preferred ultraviolet.
As UV irradiation equipment, high voltage mercury lamp, metal halide lamp, UV electrodeless lamp, LED etc. can be enumerated.
Irradiation energy can according to the kind of activation-energy-ray and the suitable setting of proportioning composition, and as an example, when enumerating the situation using high voltage mercury lamp, the irradiation energy in preferred UV-A region is 100 ~ 5,000mJ/cm 2, more preferably 200 ~ 1,000mJ/cm 2.
When being cured by electron rays, as spendable electron rays (EB) irradiating unit, various device can be used, such as can enumerate, the device etc. of Cockcroft Walton type, Vande Graaff type and resonant transformer type, as electron rays, preferably apply the energy of 50 ~ 1000eV, more preferably 100 ~ 300eV.
The hardness of the cured film using the present composition to obtain and excellent scratch resistance.Such as, the pencil hardness measured based on JIS K 5600-5-4 is generally more than 8H, can suppress the scratch caused because of the contact with metal parts etc.The material with above-mentioned cured film can utilize its characteristic and for various uses.
Such as can enumerate the various prism such as housing, glasses of the indicating meter of display panel used front panel, building materials purposes, lighting fixtures, portable phone and smart mobile phone etc. or housing, family's electrical article.
As the concrete example of display panel used front panel, electric light telegraph board, indicating meter, billboard, advertisement and mark etc. can be enumerated.
As use timber as the example of base material, the carpenter works such as stair, bed and furniture can be enumerated.As use metal as the example of base material, the metal productss etc. such as kitchen panel for kitchen use and Stainless steel basin can be enumerated.
Embodiment
Below, the present invention is illustrated based on embodiment.Be explained, the present invention is not limited to these embodiments.
In addition, " part " in following refers to " weight part ", and " % " refers to " % by weight ".
1. the manufacture of composition (A)
Production Example 1 (manufacture of MAC-TQ)
1-propyl alcohol 150g and tetramethoxy-silicane (hereinafter referred to as " the TMOS ") 36.53g (0.24mol) of alcohol permutoid reaction is loaded in the reactor possessing stirrer and thermometer, then by them while stir, slowly add 25% Tetramethylammonium hydroxide methanol solution 4.37g (methyl alcohol 0.1mol on one side, Tetramethylammonium hydroxide 12mmol), react 6 hours under temperature 25 DEG C, pH9.Then, make internal temperature be 60 DEG C, stir and react 1 hour again.At this, by reaction solution with gas chromatographic analysis (TCD detector), result, detects each compound of 1 substituent, 2 substituents, 3 substituents or 4 substituents that 1 ~ 4 methoxyl group contained in TMOS is replaced by positive propoxy and unreacted TMOS.Only detect the TMOS of trace.The ratio containing positive propoxy compound (organoalkoxysilane containing positive propoxy) in them adds up to basic 100%.Based on the peak area of the product in gas-chromatography, obtain the replacement number (every 1 molecule is containing the mean number of the positive propoxy in positive propoxy compound) of 1-propyl alcohol, result is 2.7.
Then, in above-mentioned reaction solution, add 3-methacryloxypropyl trimethoxy silane 59.62g (0.24mol), then add water 30.2g.Then, add 25% Tetramethylammonium hydroxide-methanol solution 7.88g (methyl alcohol 0.18mol, Tetramethylammonium hydroxide 21.6mmol), stir, while react 24 hours under temperature 25 DEG C, pH9.Then, add 10% aqueous nitric acid 22.2g (35.3mmol) to neutralize.Then, in the mixed solution of 120g Di Iso Propyl Ether and 180g water, add this neutralizer to extract.By washing this di-isopropyl ether layer, removing salt and excessive acid, then, add N-nitrosophenylhydroxylamine aluminium salt " Q-1301 " (trade(brand)name) 11.5mg as the Wako Pure Chemical Industries, Ltd. of stopper.From the di-isopropyl ethereal solution obtained, under reduced pressure distillation removing organic solvent, obtains water white solid organosilicon compound (hereinafter referred to as " MAC-TQ ").Its receipts amount is 57.72g.
With 1h-NMR analyzes MAC-TQ, and results verification is the polycondensate stoichiometrically being reacted with the organoalkoxysilane containing positive propoxy being used as compound (a2) by the 3-methacryloxypropyl trimethoxy silane being used as compound (a1) and obtain.
By MAC-TQ's 1containing of the alkoxyl group (with the positive propoxy of silicon atom bonding) that H-NMR figure calculates is proportional, relative to the alkoxyl group total amount contained in raw material, is equivalent to the amount of 2.5%.
In addition, measured the molecular-weight average of MAC-TQ, result by gel permeation chromatography (GPC), the Mn converted by polystyrene standard is 9600.
2. the manufacture of composition (B)
Production Example 2 (manufacture of HDI-M305)
The mixture (containing PETri0.3mol and PETet0.2mol) being loaded as pentaerythritol triacrylate (hereinafter referred to as " PETri ") and tetramethylol methane tetraacrylate (hereinafter referred to as " PETet ") is blown in the 0.5L separating bottle of pipe to possessing whipping appts and air, " ア ロ ニ ッ Network ス M-305 " (trade(brand)name of East Asia synthesis society, hereinafter referred to as " M-305 ") 159.2g, 2, 6-di-tert-butyl-4-methy phenol (hereinafter referred to as " BHT ") 0.092g and dibutyl tin laurate (hereinafter referred to as " DBTL ") 0.055g, liquid temperature is set as 70 ~ 75 DEG C, then while they are stirred, while instill hexamethylene diisocyanate (hereinafter referred to as " HDI ") 25.2g (0.15mol), make it react.
After the instillation of HDI terminates, internal temperature is set to 80 DEG C, then continues reaction, stir 3 hours.Subsequently, disappeared by IR (infrared absorption) the analysis confirmation isocyanate group of reaction product, termination reaction.Below, this reaction product is called " HDI-M305 ".
HDI-M305 is containing as the carabamate adducts (b1) of the reaction product of PETri and HDI and the PETet (being equivalent to compound (b2)) that do not react with HDI, and their weight ratio (b1): the mixture of (b2)=6:4.
3. the manufacture of active energy ray-curable coating composition and evaluation
Use the composition shown in MAC-TQ and HDI-M305 obtained above and table 1, manufacture active energy ray-curable coating composition, for various evaluation.
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, stir at normal temperatures, mix, prepare active energy ray-curable coating composition.
Then, the viscosity of 25 DEG C of each composition obtained by E type viscometer determining, is remembered in each table in the lump by the value obtained.
Then, by a side surface of the polyethylene terephthalate film of each composition lowering in 7cm × 15cm × 50 μm, cover thereon and be made up of and the mold release film of the thickness 50 μm of transmitting UV polyethylene terephthalate.Then, the thickness after solidification is made to be about 50 μm by pressure layer roller, the thickness of adjustment film.Also same method is adopted to form film at the another side of polyethylene terephthalate film.Then, across mold release film, carry out uviolizing under the following conditions, make cured film on the two sides of polyethylene terephthalate film.
Uviolizing uses the ultraviolet irradiation machine (high voltage mercury lamp) of ア イ グ ラ Off ィ ッ Network ス society, with lamp height 19cm, line speed 2.3m/ minute, irradiates in one side unipath.The irradiation energy of every path is measured by the photometer " UV POWER PUCK " of EIT society, and result, the irradiation energy in UV-A region is 900mJ/cm 2.In addition, in UV-A region, peak illumination is 170mW/cm 2.
To the cured film obtained, by method evaluation pencil hardness, scuff resistance and adaptation shown below.Their evaluation result is shown in table 2.
(1) pencil hardness
Pencil hardness is measured based on JIS K 5600-5-4.
(2) scuff resistance
On the surface of cured film, under the state of the Steel Wool " ボ Application ス タ-#0000 " of the Japanese steelwool Inc. of configuration, apply 1200g/4cm 2load, calculate cut number during double rubs 400 times.Use this cut number, based on following benchmark evaluation scuff resistance.At this,
To evaluate " A " or " B ", to be set to scuff resistance good.
A: do not have cut completely.
B: have 1 ~ 9 cut.
C: the cut having more than 10.
[table 2]
Although each composition of embodiment 1 ~ 5 employs organic solvent, demonstrate 10850mPas or its following viscosity, viscosity is fully reduced to the degree that can apply.Confirm in addition, its cured film demonstrates the good pencil hardness of 8H ~ 10H, excellent in abrasion resistance, and scuff resistance is also excellent.Wherein, use N-vinyl formamide (NVF) as the embodiment 3 ~ 5 of composition (C), the viscosity of composition is further reduced, and is conducive to screening characteristics during various coating.
In contrast to this, comparative example 1 is not owing to containing composition of the present invention (C), and the viscosity of composition is very high, is 34400mPas, high with the necessity needing during coating to be undertaken diluting by organic solvent etc. when operating.In addition, in the comparative example 2 of unsaturated compound 1,6 hexanediol diacrylate (HDDA) using nonnitrogenous atom, result, pencil hardness and the scuff resistance of cured film all reduce.
Comparative example 3 and 4 is the experimental example of the situation of content outside specialized range of the present invention of present component (C).In the comparative example 3 that the content of composition (C) is very few, fully can not reduce the viscosity of composition, otherwise in the comparative example 4 that the content of composition (C) is too much, pencil hardness and the scuff resistance of cured film 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, stirs at normal temperatures, mixes, prepare active energy ray-curable coating composition.Be explained, the composition of comparative example 5 is identical with the composition of comparative example 1.Measure the viscosity of each composition, according to the benchmark distinguished by the following stated, measure coating adaptive.Its result is remembered in the lump in table 3.
A: viscosity is more than 100mPas 10, below 000mPas
B: viscosity is greater than 10,000mPas and 15, below 000mPas
C: viscosity is greater than 15,000mPas and 20, below 000mPas
D: viscosity is greater than 20,000mPas
Then, operate similarly to Example 1, form cured film on the two sides of polyethylene terephthalate film.Subsequently, except above-mentioned (1) hardness and (2) scuff resistance, the evaluation of following (3) shock resistance is carried out.These evaluation results are shown in table 3.
(3) shock resistance (fall sphere test)
The height of the surperficial 10cm of self cure film falls the 25g iron ball based on JIS B 1501.When cured film does not produce cut and crackle, the height of each rising 5cm repeats the operation falling iron ball, and record can not produce the maximum of the height of cut and crackle.This test being carried out to 5 cured articles, evaluating shock resistance by calculating the mean value not producing the maximum of cut and crackle.
Be explained, test and implement under 23 DEG C of fixed temperature and humidity conditions with 50%RH.
[table 3]
In addition, the viscosity of each composition of embodiment 6 ~ 11 is also fully reduced to the degree that can apply.And then confirm, the cured film obtained all demonstrates the good pencil hardness of 8H ~ 10H, and scuff resistance and shock resistance (fall sphere test) are also excellent.Particularly use the embodiment 9 ~ 11 of 2 kinds containing NVF as composition (C), the viscosity of composition is low, coating operation is easy.
On the other hand, comparative example 5 is that its viscosity is high not containing the experimental example of the composition of present component (C), although the hardness of the cured film obtained and scuff resistance excellence, the value of fall sphere test is low, and be 15cm, shock resistance is poor.
Industrial applicability
Active energy ray-curable coating composition of the present invention is applicable to the coating of the various base materials such as timber, metal, inorganic materials and plastics.

Claims (7)

1. active energy ray-curable coating composition, it contains:
(A) silicoorganic compound; the silicon compound (a2) that the silicon compound (a1) containing (methyl) acryl represented by following general formula (1) and following general formula (2) represent obtains in the ratio hydrolytie polycondensation relative to above-mentioned silicon compound (a1) 1mol above-mentioned silicon compound (a2) 0.3 ~ 1.8mol
In general formula (1), R 1for the organic group with aryl of the alkyl of carbon number 1 ~ 6, the aralkyl of carbon number 7 ~ 10 or carbon number 6 ~ 10, R 2for the divalent saturated hydrocarbyl of carbon number 1 ~ 6, R 3for hydrogen atom or methyl, X is hydrolization group, and multiple X can be same to each other or different to each other, and n is 0 or 1,
SiY 4···(2)
In general formula (2), Y is that siloxane bond generates group, 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 3 valencys more than aliphatic polyol derivative, there are more than 2 (methyl) acryls and the addition reaction of (methyl) acrylate and polyisocyanates with more than 1 hydroxyl obtains, (methyl) acrylate (b2) be by 3 valencys more than aliphatic polyol derivative, there are more than 3 (methyl) acryls and not there is (methyl) acrylate of hydroxyl,
And
(C) there is in the molecule except mentioned component (A) and mentioned component (B) the free-radical polymerised unsaturated compound of nitrogen-atoms,
The content of mentioned component (A), mentioned component (B) and mentioned component (C) with they add up to 100 weight part time, mentioned component (A) is 5 ~ 50 weight parts, mentioned component (B) is 30 ~ 90 weight parts, and mentioned component (C) is 5 ~ 35 weight parts.
2. active energy ray-curable coating composition according to claim 1, wherein, above-claimed cpd (a1) is that the X in general formula (1) is alkoxyl group and n is the compound of 0, and above-claimed cpd (a2) is the Y in general formula (2) is the compound of alkoxyl group.
3. the active energy ray-curable coating composition described in claim 1 or 2, wherein, mentioned component (C) is containing at least a kind of compound (C1) be selected from containing morpholinyl monomer, amide-containing monomer and lactam compound.
4. active energy ray-curable coating composition according to claim 3, wherein, above-claimed cpd (C1) is for being selected from acryloyl morpholine, N-vinyl formamide, N-vinyl acetamide and N-vinyl-Epsilon-caprolactam at least a kind.
5. the active energy ray-curable coating composition described in any one of Claims 1 to 4, wherein, mentioned component (C) is containing the compound (C2) with tricarbimide system ring, and the content of this compound (C2) is 5 ~ 30 weight parts.
6. active energy ray-curable coating composition according to claim 5, wherein, above-claimed cpd (C2) is the free-radical polymerised unsaturated compound by oxirane or caprolactone modification.
7. the active energy ray-curable coating composition described in any one of claim 1 ~ 6, wherein, when the total of mentioned component (A), mentioned component (B) and mentioned component (C) is set to 100 weight part, the content of mentioned component (C) is 10 ~ 35 weight parts
Mentioned component (C) containing be selected from containing morpholinyl monomer, amide-containing monomer and lactam compound at least a kind of compound (C1) and there is the compound (C2) of tricarbimide system ring, when both totals are set to 10 ~ 35 weight part, above-claimed cpd (C1) containing proportional be 5 ~ 30 weight parts, above-claimed cpd (C2) containing proportional be 5 ~ 30 weight parts.
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