CN105612227B - Coating composition and coated article - Google Patents
Coating composition and coated article Download PDFInfo
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- CN105612227B CN105612227B CN201480049961.XA CN201480049961A CN105612227B CN 105612227 B CN105612227 B CN 105612227B CN 201480049961 A CN201480049961 A CN 201480049961A CN 105612227 B CN105612227 B CN 105612227B
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- hydroxy acryl
- acid
- acryl acid
- acid resin
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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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/064—Copolymers with monomers not covered by C09D133/06 containing anhydride, COOH or COOM groups, with M being metal or onium-cation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen
- C08G18/4615—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen
- C08G18/4638—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
- C08G18/4661—Polycondensates having carboxylic or carbonic ester groups in the main chain having heteroatoms other than oxygen containing nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring containing three nitrogen atoms in the ring
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
-
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret 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
- 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
- C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
- C08G18/78—Nitrogen
- C08G18/7806—Nitrogen containing -N-C=0 groups
- C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
- C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate groups
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (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)
Abstract
The present invention provides a kind of coating composition, it includes the host containing hydroxy acryl acid resin (A) and the curing agent containing polyisocyanate compound (B), the hydroxy acryl acid resin (A) is 70~200mgKOH/g containing hydroxyl value on the basis of the resin solid quality in host, glass transition temperature is less than 30 DEG C of the mass parts of hydroxy acryl acid resin (A1) 25~95, and hydroxyl value is 30~200mgKOH/g, glass transition temperature is 30~75 DEG C of the mass parts of hydroxy acryl acid resin (A2) 5~75, and hydroxy acryl acid resin (A2) has specific monomer composition.
Description
Technical field
The present invention relates to a kind of coating composition and coated article, its can be formed have relative to plastic basis material it is excellent resistance to
Scratch resistance, hardness, outward appearance, the film of tack and chemical-resistant.
Background technology
In recent years, ABS resin has been used in the various industrial products such as communication equipment, family's electrical article, automobile using part, has been gathered
The plastic basis materials such as propylene, polyurethane resin, polycarbonate resin.Marresistance, hardness, outward appearance, attached is required the industrial product
The property, chemical-resistant etc..
In various industrial products, it is the coating excellent to the tack of base material, the second layer as base material to have using first layer
The different multiple coating of the overlapping coating function of mode of the coating of excellent scratch resistance and form the industrial product of multilayer film, its
In, also require full in the coating process for once toasting (application is once sintered) is once coated with using a kind of coating
The industrial product of sufficient tack and various film performances, as problem, it is desirable to be once coated with and once toast more difficulty.In addition,
As chemical-resistant, particularly liquid foundation cream, sun screen, concealer, suncream, beautifying liquid, emulsion, handguard are required in recent years
Composition for external application containing ultra-violet absorber, preservative and emulsifying agent etc. as the cosmetics such as frost is even in being attached to
Placed in the state of coated surface will not also occur film attachment is bad, outward appearance reduces and hardness reduces etc. (it is following, slightly remember sometimes
For " for the patience of the composition containing ultra-violet absorber etc. ").
Such as in patent document 1, the coating excellent as traumatic resistance and acid resistance, disclose a kind of automotive clear
Coating composition, it is the clear coating composition containing hydroxy acryl acid resin and polyfunctional isocyanate compound, its
It is characterised by, the hydroxy acryl acid resin is (methyl) acrylic acid hydroxyl using the hydroxy alkyl with carbon number 4~9
Base Arrcostab is as hydroxy acryl acid resin obtained from least one of monomer, the polyfunctional isocyanate compound
In at least a portion be isocyanurate type isocyanate compound, relative to the hydroxy acryl acid resin and multifunctional
The total solid of isocyanate compound has 25~50 mass % specific soft chain segment portion, contains internal ester monomer so as to be derived from
Soft chain segment portion relative to the hydroxy acryl acid resin and the total solid of polyfunctional isocyanate compound ratio
The mode for the scope that dynamic glass transition temperature for below 4.5 mass % and obtained cured coating film is 30~60 DEG C is entered
It is prepared by row.
However, the coating is primarily adapted for metal base, coating process is once toasted relative to the once coating of plastic basis material
In tack and insufficient relative to the patience of the composition containing ultra-violet absorber etc..
In patent document 2, as resistance to carwash scratch resistant, acid resistance, the coating having excellent weather resistance, a kind of coating is disclosed
Composition, it using hydroxyl value is 80~220mgKOH/g that it, which is, glass transition temperature less than 0 DEG C and contains 25 as -50 DEG C
The hydroxy-containing resin (A) of~55 mass % unit from (methyl) acrylic acid 4- hydroxybutyls, hydroxyl value be 80~
220mgKOH/g, the hydroxy-containing resin (B) that glass transition temperature is 0~50 DEG C and it is made up of polyisocyanate compound
Crosslinking agent (C) is the coating composition of required composition, it is characterised in that hydroxy-containing resin (A) and hydroxy-containing resin (B's) contains
Ratio is calculated as 95/5~50/50 with resin solid quality ratio, and relative as the NCO of the functional group of crosslinking agent (C)
In the content ratio of hydroxy-containing resin (A) and total hydroxyl of hydroxy-containing resin (B) using NCO/OH molar ratio computing as 0.5~1.5.
However, the coating is primarily adapted for metal base, coating process is once toasted relative to the once coating of plastic basis material
In tack, insufficient relative to the patience of the composition containing ultra-violet absorber etc..
In patent document 3, a kind of self-healing coating composition is disclosed, it is characterised in that contain lactone-modified propylene
Acid resin and PCDL.Although the coating resin composition is in once baking coating process is once coated with to ABS plates
Excellent scratch resistance, it is but insufficient relative to the patience of the composition containing ultra-violet absorber etc..
In patent document 4, a kind of coating resin composition is disclosed, it is characterised in that with both ratio [more isocyanides
The molal quantity of NCO in ester compound]/[molal quantity of the hydroxyl in acrylic acid series multiple alcohol (B)] be 0.75~
Ratio as 1.5 scope contains polyisocyanate compound (A) and acrylic acid series multiple alcohol (B), wherein polyisocyanates
The NCO equivalent of compound (A) is 100~280g/eq scope, and the average glass of acrylic acid series multiple alcohol (B) turns
Temperature (Tg) is that -55 DEG C of average functional group numbers less than -9 DEG C, the hydroxyl of every 1 molecule are 4~20 and count equal molecule
Measure the scope that (Mn) is 3000~15000.Although the coating resin composition is right in once baking coating process is once coated with
The traumatic resistance and base material excellent adhesion of ABS plates, but do not filled relative to the patience of the composition containing ultra-violet absorber etc.
Point.
In patent document 5, a kind of coating resin composition is disclosed, it is characterised in that with both ratio [more isocyanides
The molal quantity of NCO in ester compound]/[molal quantity of the hydroxyl in PEPA (B)] be 0.75~1.5
Scope as ratio contain NCO equivalent be 100~280g/eq scope polyisocyanate compound (A) and
Average Tg is -50~-10 DEG C, the average functional group number of the hydroxyl of every 1 molecule is 4~20 and number-average molecular weight (Mn) is 1000
The PEPA (B) of~3000 scope.Although the coating resin composition is in once baking coating process is once coated with
Traumatic resistance and base material excellent adhesion to ABS plates, but relative to the composition containing ultra-violet absorber etc. patience not
Fully.
There is a kind of hardening resin composition towards hot forming film disclosed in patent document 6, it is characterised in that institute
Stating hot forming film has chemical-resistant, such as in high temperature in the state of for sun-proof emulsion, hand lotion attachment
Lower long-time exposes to the open air, and acrylic resin film surface also will not be coarse, in addition, in the situation for the formed products for being configured to deep-draw shape
Under, it will not also be cracked on film surface, and there is case hardness, the resin combination contains with carboxyl and hydroxyl, consolidated
The vinyl polymers (A) and more isocyanides that shape thing acid number is 15~150mgKOH/g, glass transition temperature is 70~140 DEG C
Ester compound (B), the content of polyisocyanate compound (B) be with the solid content hydroxyl value 2 of vinyl polymers (A)~
The content of 80mgKOH/g reactions.But should once it be toasted with the hardening resin composition of film being once coated with towards thermoforming
It is insufficient to the tack and marresistance of plastic basis material in coating process.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2006-176634 publications
Patent document 2：Japanese Unexamined Patent Publication 2009-46642 publications
Patent document 3：Japanese Unexamined Patent Publication 2012-97127 publications
Patent document 4：Japanese Unexamined Patent Publication 2012-97173 publications
Patent document 5：Japanese Unexamined Patent Publication 2012-87183 publications
Patent document 6：Japanese Unexamined Patent Publication 2012-97248 publications
The content of the invention
Invent problem to be solved
The present invention is to consider these aspects and complete, its object is to, there is provided a kind of coating composition and coated article,
Wherein, be once coated with once toast coating process in, the coating composition can be formed have relative to plastic basis material it is excellent
Marresistance, hardness, outward appearance, tack and with relative to the composition containing ultra-violet absorber etc. patience painting
Film.
For solving the technical scheme of problem
The present inventor etc. are concentrated on studies to achieve these goals, are as a result found, by using following coating groups
Compound can solve above-mentioned problem, so that completing the present invention, the coating composition contains contains specific 2 kinds with special ratios
The host of hydroxy acryl acid resin and the curing agent containing polyisocyanate compound.
That is, the present invention provides article obtained from following coating composition and the application coating composition.
The present invention relates to following (1)~(6).
(1) a kind of coating composition, it is the coating of the curing agent comprising host and containing polyisocyanate compound (B)
Composition, the host contain hydroxy acryl acid resin (A), wherein,
Hydroxy acryl acid resin (A) is contained on the basis of the resin solid quality in host
The hydroxyl value of 25~95 mass parts is the hydroxyl third of 70~200mgKOH/g, glass transition temperature less than -30 DEG C
Olefin(e) acid resin (A1) and
The hydroxyl third that the hydroxyl value of 5~75 mass parts is 30~200mgKOH/g, glass transition temperature is -30~75 DEG C
Olefin(e) acid resin (A2),
And
The hydroxy acryl acid resin (A2) is using polymerism unsaturated monomer (a2-1)~(a2-3) total amount as base
Standard, make 30~80 mass % methyl methacrylate (a2-1), 10~35 mass % hydroxyl polymerism unsaturated monomer
(a2-2) and 0~60 mass % other polymerism unsaturated monomers (a2-3) reaction obtained from hydroxy acryl acid tree
Fat.
(2) coating composition according to above-mentioned (1), wherein,
The hydroxy acryl acid resin (A1) is using polymerism unsaturated monomer (a1-1) and (a1-2) total amount as base
Standard, make the polymerism unsaturated monomer (a1-1) and 40~90 of 10~60 mass % hydroxy alkyl with carbon number 4~9
Hydroxy acryl acid resin obtained from quality % other polymerism unsaturated monomers (a1-2) reaction.
(3) coating composition according to above-mentioned (1) or (2), wherein, polyisocyanate compound (B) be selected from by
It is at least one kind of in the group that biuret form and the polyisocyanate compound of allophanic acid ester type are formed.
(4) coating composition according to any one of above-mentioned (1)~(3), wherein, host also contains hydroxyl polyester
Resin (C).
(5) a kind of coating process, wherein the coating on plastic basis material face any one of application above-mentioned (1)~(4)
Composition.
(6) a kind of coated article, it is by any one of application above-mentioned (1)~(4) on plastic basis material face
Obtained from coating composition.
Invention effect
According to the coating composition of the present invention, can be formed in once baking coating process is once coated with relative to plastics base
Material is with excellent marresistance, hardness, outward appearance, tack and with relative to the composition containing ultra-violet absorber etc.
The film of patience.
Embodiment
Hereinafter, the coating composition of the present invention is illustrated in further detail.
It should be noted that in this manual, " quality " refers to " weight ".
The coating composition of the present invention is comprising the host containing hydroxy acryl acid resin (A) and contains polyisocyanates
The coating composition of the curing agent of compound (B), wherein, the hydroxy acryl acid resin (A) is with the resin solid in host
Contain specific hydroxy acryl acid resin (A1) and specific hydroxy acryl acid resin on the basis of amount of substance with special ratios
(A2)。
(host)
<Hydroxy acryl acid resin (A)>
In the present invention, hydroxy acryl acid resin (A) refers to the acrylic resin containing hydroxyl in molecule.Hydroxyl third
Olefin(e) acid resin (A) is using conventional method by making hydroxyl polymerism unsaturated monomer and other copolymerizable polymerism insatiable hungers
Synthesized with monomer copolymerization.
As hydroxyl polymerism unsaturated monomer, such as can enumerate：(methyl) acrylic acid 2- hydroxy methacrylates, (methyl)
Acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, (methyl) acrylic acid 4- hydroxybutyls, polyethyleneglycol (first
Base) polyalcohol such as acrylate, polypropylene glycol (methyl) acrylate and (methyl) acrylic acid monoesters compound or by ε-oneself in
Compound that the monoesters compound ring-opening polymerisation of ester and the polyalcohol and (methyl) acrylic acid forms etc., these can individually make
With or be used in combination of two or more.
As other copolymerizable polymerism unsaturated monomers, such as can enumerate：(methyl) methyl acrylate, (first
Base) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl)
Isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) propylene
Sour 2- ethylhexyls, (methyl) cyclohexyl acrylate, (methyl) n-octyl, (methyl) acrylic acid nonyl ester, (methyl) third
The Arrcostab of (methyl) acrylic acid such as olefin(e) acid Lauryl Ester, (methyl) isobornyl acrylate, (methyl) stearyl acrylate base ester；
The unsaturated monomer of polymerism containing carboxyl such as (methyl) acrylic acid, maleic acid, maleic anhydride；(methyl) acrylic acid N, N- dimethylamino
(methyl) such as base ethyl ester, (methyl) acrylic acid N, N- diethylamino ethyl ester, (methyl) acrylic acid N, N- dimethylamino propyl ester
Acrylate；Acrylamide, Methacrylamide, N, N- dimethyl aminoethyls (methyl) acrylamide, N, N-
Diethylamino ethyl (methyl) acrylamide, N, N- dimethylaminopropyls (methyl) acrylamide, N- methylol acryloyls
Amine, N hydroxymethyl acrylamide methyl ether, N hydroxymethyl acrylamide butyl ether etc. (methyl) acrylamide or derivatives thereof；2-
(methacryloxy) ethyl-trimethyl salmiac, 2- (methacryloxy) ethyMmethylammonium bromide etc. contain quaternary ammonium salt
The monomer of base；(methyl) acrylamide-alkanesulfonic acids such as 2- acrylamide -2- methyl propane sulfonic acids, (methyl) acrylic acid 2- sulphurs
Base ethyl ester etc. (methyl) sulfoethyl Arrcostab；Acrylonitrile, methacrylonitrile, vinyl acetate, styrene, vinyl first
The polymerisms containing aromatic rings such as benzene, α-methylstyrene unsaturated monomer；More vinyl compounds such as ALMA；
γ-(methyl) acryloxypropyl trimethoxy silane, γ-(methyl) acryloxypropyl triethoxysilane, γ-
Polymerism unsaturated monomers containing hydrolyzable silyl group such as (methyl) acryloxypropyl dimethoxysilane etc., this
A bit can individually using or be used in combination of two or more.
In addition, in this manual, " (methyl) acrylate " refers to acrylate or methacrylate, " (methyl)
Acrylic acid " refers to acrylic or methacrylic acid.In addition, " (methyl) acryloyl group " refers to acryloyl group or methacryl
Base, " (methyl) acrylamide " refer to acrylamide or Methacrylamide.
The copolymerization of above-mentioned polymerism unsaturated monomer is preferably based on the copolymerization of solution polymerization process, such as can enumerate：Make
The mixture of polymerism unsaturated monomer and radical polymerization initiator dissolves or is scattered in organic solvent, generally at about 80 DEG C
Stirred 1~10 hour or so at a temperature of~about 200 DEG C while heating the method for polymerizeing it.
In the present invention, from the marresistance of obtained film, hardness, outward appearance, tack and relative to containing ultraviolet
The viewpoints such as the patience of the composition of absorbent etc. consider that hydroxy acryl acid resin (A) contains specific hydroxy acryl acid tree
Fat (A1) and specific hydroxy acryl acid resin (A2).
In the coating composition of the present invention, from the marresistance of obtained film, hardness, outward appearance, tack and relative
Consider in viewpoints such as the patience of the composition containing ultra-violet absorber etc., preferably above-mentioned hydroxy acryl acid resin (A1) and upper
The match ratio (mass ratio) for stating hydroxy acryl acid resin (A2) is the former (A1)/the latter (A2)=25/75~95/5, is preferably
30/70~80/20, more preferably 40/60~70/30.
In the present invention, it is (resistance to sun-proof from the marresistance of obtained film, hardness, outward appearance, tack and chemical-resistant
Agent) etc. viewpoint consider, on the basis of total resin solid quality in host, the content of hydroxy acryl acid resin (A1) is
25~95 mass parts, preferably 30~60 mass parts, more preferably 40~50 mass parts.
In the present invention, it is (resistance to sun-proof from the marresistance of obtained film, hardness, outward appearance, tack and chemical-resistant
Agent) etc. viewpoint consider, on the basis of total resin solid quality in host, the content of hydroxy acryl acid resin (A2) is
5~75 mass parts, preferably 10~50 mass parts, more preferably 15~45 mass parts.
<<Hydroxy acryl acid resin (A1)>>
In the present invention, hydroxy acryl acid resin (A1) be hydroxyl value be 70~200mgKOH/g, be preferably 100~
200mgKOH/g, more preferably 120~180mgKOH/g and glass transition temperature are less than -30 DEG C, preferably shorter than -40
DEG C, even more preferably below -50 DEG C of hydroxy acryl acid resin.If the hydroxyl value of hydroxy acryl acid resin (A1) is
More than 70mgKOH/g, then tack, hardness and the outward appearance of the film obtained become good, if hydroxyl value is below 200mgKOH/g,
Then the marresistance of film becomes good, so being preferable.In addition, if glass transition temperature applies sometimes more than -30 DEG C
The marresistance of film is deteriorated.
It should be noted that in this manual, the glass transition temperature Tg of hydroxy acryl acid resin is by following
The value that formula calculates.
1/Tg (K)=W1/T1+W2/T2+Wn/Tn
Tg (DEG C)=Tg (K) -273
In formula, W1, W2, Wn are the mass fraction of each monomer, and T1, T2Tn are the homopolymer of each monomer
Glass transition temperature Tg (K).
It should be noted that the glass transition temperature of the homopolymer of each monomer be based on
POLYMERHANDBOOKFourthEdition, J.Brandrup, E.h.Immergut, E.A.Grulke compile (1999 years) and obtained
Value, the glass transition temperature for the monomer do not recorded in the document uses following value：By the homopolymer of the monomer to divide equally again
Son amount is synthesized for 50,000 or so mode, and value during its glass transition temperature is determined by differential scanning type heat analysis.
In addition, in this manual, weight average molecular weight and number-average molecular weight are the value tried to achieve in the following manner：It will use
(holding capacity) utilizes standard known to the molecular weight measured in identical conditions between the Bao Chi Time that gel permeation chromatography (GPC) measures
The retention time (holding capacity) of polystyrene is scaled the molecular weight of polystyrene.Pillar use " TSKgel G-4000H ×
L ", " TSKgel G-3000H × L ", " TSKgel G-2500H × L ", " TSKgel G-2000H × L " (are eastern Cao (strain) public affairs
Department manufacture, trade name) this 4, mobile phase be tetrahydrofuran, measurement temperature is 40 DEG C, flow velocity is 1ml/ minutes, detector is
Carried out under conditions of RI.
Hydroxy acryl acid resin (A1) passes through the hydroxy alkyl that makes to have carbon number 4~9 using conventional method
Polymerism unsaturated monomer (a1-1) and other polymerism unsaturated monomers (a1-2) are copolymerized and synthesized.
As the polymerism unsaturated monomer (a1-1) of the hydroxy alkyl with carbon number 4~9, can enumerate：(first
Base) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 5- hydroxyls pentyl ester, the own ester of (methyl) acrylic acid 6- hydroxyls, (methyl) propylene
Sour 7- hydroxyls heptyl ester, (methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) acrylic acid 7- methyl -8- hydroxyls monooctyl ester, (methyl) propylene
Sour 2- methyl -8- hydroxyls monooctyl ester, (methyl) acrylic acid 9- hydroxyl nonyl esters etc., these can individually use or will be two or more
It is applied in combination.Wherein, from marresistance, outward appearance, tack and the patience relative to the composition containing ultra-violet absorber etc.
From the viewpoint of excellent, particularly preferred (methyl) acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 5- hydroxyls pentyl ester, (methyl) third
The own ester of olefin(e) acid 6- hydroxyls.
As other polymerism unsaturated monomers (a1-2), above-mentioned hydroxy acryl acid resin (A) column can be suitably used
Described in monomer in monomer (a1-1) beyond monomer.Wherein, from obtain low Tg hydroxy acryl acid resin (A1),
To marresistance, hardness, outward appearance, tack and relative to the excellent film of the patience of the composition containing ultra-violet absorber etc.
From the viewpoint of, as other polymerism unsaturated monomers (a1-2), particularly preferably include the alkyl with carbon number 4~8
Polymerism unsaturated monomer.In the present invention, " the polymerism unsaturated monomer with the alkyl of carbon number 4~8 " refers to
The carbon number of moieties is 4~8 unsaturated monomer of polymerism containing alkyl.As the alkyl with carbon number 4~8
Polymerism unsaturated monomer, it can enumerate：(methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid
The tert-butyl ester, (methyl) acrylic acid n-pentyl ester, (methyl) the just own ester of acrylic acid, (methyl) n-octyl, (methyl) acrylic acid
2- ethylhexyls etc..These monomers can individually using or be used in combination of two or more.Wherein, from obtained film
The consideration of the viewpoints such as marresistance, hardness, outward appearance, tack and the patience relative to the composition containing ultra-violet absorber etc.,
Particularly preferably (methyl) n-butyl acrylate, 2-EHA.
The polymerization of the hydroxy alkyl with carbon number 4~9 during on manufacturing above-mentioned hydroxy acryl acid resin (A1)
The use ratio of property unsaturated monomer (a1-1), with monomer component (polymerism unsaturated monomer (a1-1) and (a1-2)) total amount
On the basis of, preferably 10~60 mass %, more preferably 15~50 mass %, further preferred 20~40 mass %.
The use of other polymerism unsaturated monomers (a1-2) during on manufacturing above-mentioned hydroxy acryl acid resin (A1)
Ratio, on the basis of the total amount of monomer component, preferably 40~90 mass %, more preferably 50~85 mass %, further preferably
60~80 mass %.
Using, the polymerism unsaturated monomer of the alkyl with carbon number 4~8 is unsaturated single as other polymerisms
In the case of body (a1-2), on the basis of the total amount of monomer component, its use ratio preferably 10~80 mass %, more preferably 15~
70 mass %, further preferred 20~65 mass %.
In the present invention, from marresistance, hardness, outward appearance, tack and relative to the group containing ultra-violet absorber etc.
The viewpoints such as the patience of compound consider, the weight average molecular weight of hydroxy acryl acid resin (A1) preferably 5,000~33,000 model
In enclosing, further preferably in the range of 8,000~30,000.
<<Hydroxy acryl acid resin (A2)>>
In the present invention, hydroxy acryl acid resin (A2) be hydroxyl value be 30~200mgKOH/g, be preferably 50~
180mgKOH/g, more preferably 100~160mgKOH/g and glass transition temperature are -30~75 DEG C, are preferably -20
~50 DEG C, more preferably -10~40 DEG C of hydroxy acryl acid resin.
In addition, hydroxy acryl acid resin (A2) contains polymerism unsaturated monomer (a2-1)~(a2-3), with each monomer
(a2-1) on the basis of~(a2-3) total amount, by obtaining following substance reaction：Methyl methacrylate (a2-1) 30~
80 mass %, preferably 32~75 mass %, further preferred 35~70 mass %；Hydroxyl polymerism unsaturated monomer (a2-2)
10~35 mass %, preferably 15~30 mass %, further preferred 20~28 mass %；And other polymerism unsaturated monomers
(a2-3) 0~60 mass %, preferably 0~53 mass %, further preferred 2~45 mass %.
If the hydroxyl value of hydroxy acryl acid resin (A2) is more than 30mgKOH/g, relative to containing ultra-violet absorber
Deng the patience of composition become good, if hydroxyl value is below 200mgKOH/g, the marresistance of obtained film becomes good
It is good, so being preferable.In addition, if glass transition temperature is more than -30 DEG C, the tack of film is good, and relatively
Become good in the patience of the composition containing ultra-violet absorber etc., if less than 75 DEG C, then the marresistance of film becomes
Well, so being preferable.If in addition, on the basis of the total amount of each monomer, the content of methyl methacrylate (a2-1) is 30
~80 mass %, then the marresistance of film and tack become good, and relative to the group containing ultra-violet absorber etc.
The patience of compound becomes good.
As hydroxyl polymerism unsaturated monomer (a2-2), can enumerate in above-mentioned hydroxy acryl acid resin (A) column
The hydroxyl polymerism unsaturated monomer of record.
As other polymerism unsaturated monomers (a2-3), above-mentioned hydroxy acryl acid resin (A) column can be suitably used
Described in other copolymerizable polymerism unsaturated monomers in methyl methacrylate and hydroxyl polymerism unsaturated monomer
(a2-2) monomer beyond.
In the present invention, from marresistance, hardness, outward appearance, tack and relative to the group containing ultra-violet absorber etc.
The viewpoints such as the patience of compound consider, the weight average molecular weight of hydroxy acryl acid resin (A2) preferably 5,000~33,000 model
In enclosing, further preferably in the range of 8,000~30,000.
In the coating composition of the present invention, hydroxy acryl acid resin (A) can also contain above-mentioned hydroxy acryl acid
Hydroxy acryl acid resin beyond resin (A1) and above-mentioned hydroxy acryl acid resin (A2).
<Other host compositions>
The present invention host using hydroxy acryl acid resin (A) as must composition, the hydroxy acryl acid resin (A) with
Special ratios contain hydroxy acryl acid resin (A1) and hydroxy acryl acid resin (A2), and the host of the present invention can be entered
One step contains hydroxyl group containing polyester resin (C), hydroxyl polyurethane resin, phenolic resin, polycarbonate resin and ring as needed
The resin components such as oxygen tree fat.
<<Hydroxyl group containing polyester resin (C)>>
Above-mentioned hydroxyl group containing polyester resin (C) can generally utilize its own known method by making polyacid and polyalcohol
Esterification is carried out in a manner of hydroxyl is excessive and is obtained.
Polyacid is the compound for having in 1 molecule more than 2 carboxyls, such as can be enumerated：Terephthalic acid (TPA), isophthalic two
The aromatic polyvalents such as formic acid, phthalic acid, naphthalene dicarboxylic acids, 4,4 '-diphenyl dicarboxylic acid, diphenyl methane -4,4 '-dicarboxylic acids acid
And its acid anhydrides；Hexahydro M-phthalic acid, hexahydro terephthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid etc. are alicyclic
Dicarboxylic acids and its acid anhydrides；Adipic acid, decanedioic acid, suberic acid, butanedioic acid, glutaric acid, maleic acid, chloromaleic acid, fumaric acid, ten
The aliphatic polybasic acids such as two docosandioic acids, pimelic acid, azelaic acid, itaconic acid, citraconic acid, dimeric dibasic acid and its acid anhydrides；These dicarboxylic acids
Methyl esters, the lower alkyl esters such as ethyl ester；Trimellitic acid, trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, trimesic acid, first
More than 3 yuan of polyacids such as cyclohexene tricarboxylic acids, tetrachloro hexene polyacid and its acid anhydrides etc..
Polyalcohol is the compound for having in 1 molecule more than 2 hydroxyls, such as can be enumerated：Ethylene glycol, propane diols, two
Ethylene glycol, trimethylene, tetraethylene glycol, triethylene glycol, DPG, 1,4- butanediols, 1,3 butylene glycol, 2,3- fourths two
Alcohol, 1,2- butanediols, 3- methyl isophthalic acids, 2- butanediols, 1,2- pentanediols, 1,5- pentanediols, 1,4- pentanediols, 2,4-PD,
2,3- dimethyltrimethylenes glycol, tetramethylene glycol, 3- methyl -4,3- pentanediols, 3- methyl -4,5- pentanediols, 2,2,
4- trimethyl -1,3- pentanediols, 1,6-HD, 1,5- hexylene glycols, 1,4- hexylene glycols, 2,5-HD, neopentyl glycol, hydroxyl
The dihydric alcohols such as pivalic acid DOPCP；The polylactone diol that the addition of the lactone such as 6-caprolactone is formed in these 2 yuan of alcohol；It is right
The esterdiol classes such as double (hydroxyethyl) esters of phthalic acid；The alkylene oxide adducts of bisphenol-A, polyethylene glycol, polypropylene glycol, poly- fourth
The PTMEG class such as glycol；The alpha-olefin epoxides, カ ー ジ ュ ラ such as expoxy propane and epoxy butane E10 [シ ェ Le chemistry
Company's manufacture, trade name, synthesize highly -branched saturated fatty acid ethylene oxidic ester] etc. mono-epoxy compounds；Glycerine, trihydroxy methyl
Propane, trimethylolethane, two glycerine, triglycerin, 1,2,6- hexanetriols, pentaerythrite, dipentaerythritol, sorbierite, sweet dew
The alcohol that more than 3 yuan of alcohol etc.；The poly-lactone polyol class that the addition of the lactone such as 6-caprolactone is formed in these more than 3 yuan alcohol；
The fat such as 1,4 cyclohexane dimethanol, Tricyclodecane Dimethanol, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F, hydrogenated bisphenol A and A Hydrogenated Bisphenol A F
Ring race polyalcohol etc..
The importing of hydroxyl for example can by and with 1 molecule the polyalcohol with more than 3 hydroxyls carry out.
In addition, in the reaction of above-mentioned polyacid and polyalcohol, can also further as needed using monoacid, oil into
Divide (also comprising the aliphatic acid) etc..As monoacid, such as can enumerate：Benzoic acid or t-butyl perbenzoate etc., as oil into
Point, such as can enumerate：Castor oil, dehydrated castor oil, safflower oil, soybean oil, linseed oil, tall oil, coconut oil and they
Aliphatic acid etc., these can use a kind or be mixed with two or more.And then polyester resin can also use butyl as needed
The epoxides such as glycidyl ether, alkyl phenyl glycidyl ethers, glycidyl neodecanoate are modified.
In the present invention, from the marresistance of obtained film, hardness, outward appearance, tack and relative to containing ultraviolet
The viewpoints such as the patience of the composition of absorbent etc. consider that it is 50~200mgKOH/ that hydroxyl group containing polyester resin (C), which it is expected comprising hydroxyl value,
G, be preferably 60~150gKOH/g, weight average molecular weight be 2,000~20,000, be preferably 2,000~15,000 hydroxyl gather
Ester resin (C1).From the marresistance of obtained film, hardness, outward appearance, tack and relative to containing ultra-violet absorber etc.
The viewpoint such as the patience of composition consider that the acid number for it is expected hydroxyl group containing polyester resin (C1) is preferably 0~10mgKOH/g, enters one
Step is preferably 0~5mgKOH/g.
And then in the present invention, from the marresistance of obtained film, hardness, outward appearance, tack and relative to containing purple
The viewpoints such as the patience of the composition of ultraviolet absorbers etc. consider that hydroxyl group containing polyester resin (C1) is preferably by polyalcohol and polynary
Hydroxyl group containing polyester resin (C1-1) obtained from the reaction of acid, wherein the polyalcohol, which includes, has urea acrylate structure (ヌ レ ー ト
Agencies makes) cyclic polyol alcoholic compound (c1).
As the cyclic polyol alcoholic compound (c1) with urea acrylate structure, such as can enumerate：Three (hydroxyethyls) are different
Three (hydroxy alkyl) isocyanuric acids such as cyanurate, three (hydroxypropyl) isocyanuric acid esters and three (hydroxybutyl) isocyanuric acid esters
Ester, three (hydroxy alkyl) isocyanuric acid ester 6-caprolactone modifier, make three (hydroxyethyl) isocyanuric acid esters, glycol chemical combination
The hydroxyl of thing and dicarboxylic acids in three (hydroxyethyl) isocyanuric acid esters and diol compound is relative to the carboxyl in dicarboxylic acids
In the state of excess react obtained from three (hydroxyethyl) isocyanuric acid esters carboxylate and make that there is urea acrylate structure
The hydroxyl of polyisocyanate compound and diol compound in diol compound is relative to more isocyanides with urea acrylate structure
Reaction product etc. obtained from being reacted in the state of NCO excess in ester compound.These can be used alone
Or it is used in combination of two or more.
Wherein, it is excellent from the viewpoint of patience of the obtained film relative to the composition containing ultra-violet absorber etc.
The 6-caprolactone modifier of three (2- hydroxyethyls) isocyanuric acid esters and three (2- hydroxyethyls) isocyanuric acid esters is selected, it is further excellent
Select three (2- hydroxyethyls) isocyanuric acid esters.
Consider from obtained film relative to viewpoints such as the patience of the composition containing ultra-violet absorber etc., it is above-mentioned to contain hydroxyl
The content ratio of the cyclic polyol alcoholic compound (c1) with urea acrylate structure in base polyester resin (C1-1) is with alcohol composition
On the basis of total amount, preferably in the range of 1~75mol%, more preferably in the range of 10~60mol%.
From the marresistance of obtained film, hardness, outward appearance, tack and relative to the group containing ultra-violet absorber etc.
The viewpoints such as the patience of compound consider that the content of hydroxyl group containing polyester resin (C1) is on the basis of the total solid in host preferably 10
In the range of~70 mass parts, more preferably in the range of 20~60 mass parts.From the marresistance of obtained film, hardness,
The consideration of the viewpoints such as outward appearance, tack and the patience relative to the composition containing ultra-violet absorber etc., hydroxyl group containing polyester resin
(C1-1) content on the basis of the total solid in host preferably in the range of 10~50 mass parts, more preferably 20~40
In the range of mass parts.
(curing agent)
Curing agent used in the present invention contains polyisocyanate compound (B).
<Polyisocyanate compound (B)>
As polyisocyanate compound (B), such as can enumerate：Hexamethylene diisocyanate, the methylene of trimethyl six
The aliphatic polyisocyante class such as group diisocyanate, dimer acid diisocyanate, lysine diisocyanate；These aliphatic
The biuret form addition product of polyisocyanates, isocyanurate ring addition product, allophanic acid ester type addition product, urea diketone type addition
Thing；IPDI, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), hexahydrotoluene -2,4- or -2,6-
The alicyclic diisocyanate class such as diisocyanate；Biuret form addition product, the isocyanuric acid of these alicyclic diisocyanates
Ester cycloaddition thing；Xylylene diisocyanate, tetramethyl xylylene diisocyanate, toluene di-isocyanate(TDI), 4,4 '-two
The aromatic diisocyanates such as methylenebis phenyl isocyanate (MDI), 1,5- naphthalene diisocyanates, 1,4- naphthalene diisocyanates
Compound；Biuret form addition product, the isocyanurate ring addition product of these aromatic diisocyanates；Hydrogenate MDI and hydrogenation MDI
Derivative；Make ethylene glycol, propane diols, 1,4- butanediols, dihydromethyl propionic acid, PAG, trimethylolpropane, oneself
The polyurethane-reinforcement that the hydroxyl of the polyalcohols such as triol is formed with the excessive ratio of NCO with polyisocyanate compound reaction
Addition product；The biuret form addition products of these polyurethane-reinforcement addition products, isocyanurate ring addition product etc..Wherein, from obtaining
The viewpoints such as marresistance, hardness, outward appearance, tack and the patience relative to the composition containing ultra-violet absorber etc. of film
Consider, can particularly preferably use biuret form addition product (the polyisocyanates chemical combination of biuret form of aliphatic polyisocyante
Thing) or allophanic acid ester type addition product (polyisocyanate compound of allophanic acid ester type).
On above-mentioned polyisocyanate compound (B) usage amount, with NCO (NCO) contained therein relative to
The NCO/OH of hydroxyl (OH) in above-mentioned host equivalent ratio is usually 0.5~2.0, be preferably 0.8~1.5 in the range of
Mode is selected more appropriate.
The present invention coating composition in, can as needed proper combination organic solvent, curing catalysts, pigment,
The coating generally used in the field of coating such as pigment dispersing agent, levelling agent, ultra-violet absorber, light stabilizer, plasticizer
With additive and it is matched with host and/or curing agent.
It is not particularly limited as above-mentioned organic solvent, such as hydrocarbon system, ester system, ether system, alcohol system, ketone system etc. can be used generally
Paint solvent.
As above-mentioned curing catalysts, such as can enumerate：Tin octoate, two (2 ethyl hexanoic acid) dibutyl tins, two (2- second
Base caproic acid) dioctyl tin, dioctyl tin diacetate, dibutyl tin laurate, Dibutyltin oxide, dioctyl tin oxide, two
Butyl tin soap, 2 ethyl hexanoic acid lead, zinc octoate, zinc naphthenate, fatty acid zinc class, cobalt naphthenate, calcium octoate, aphthenic acids
The organo-metallic compounds such as copper, metatitanic acid four (2- ethylhexyls) ester, these can use a kind or be mixed with two or more.These
Can also further as needed and the urethane cures catalyst known to tertiary amine, phosphate cpd etc..In the painting of the present invention
In the case that feed composition contains curing catalysts, the usage amount of curing catalysts is commonly angled relative to the resin in coating composition
The mass parts of solid content 100 are 0.001~2 mass parts, are appropriate preferably in the range of 0.01~1 mass parts.
As above-mentioned pigment, such as can enumerate：Titanium oxide, zinc white, carbon black, cadmium red, chrome vermillion, chrome yellow, chromium oxide, Pu Lu
Scholar's indigo plant, cobalt blue, AZOpigments, phthalocyanine color, quinacridone pigment, isoindoline pigment, intellectual circle's series pigments, perylene pigment
Deng coloring pigment；The extender pigments such as talcum, clay, kaolin, barium monoxide, barium sulfate, barium carbonate, calcium carbonate, aluminum oxide be white；Aluminium
Powder, mica powder, with aoxidizing metallic pigments such as titanium coated mica powder etc..These pigment can be used alone or by two kinds
Combination of the above uses.
In the case where the coating composition of the present invention uses as clear dope, when containing pigment, the cooperation of pigment
Amount will not preferably hinder the amount of the transparent degree of obtained film, such as with the matter of solid content 100 in coating composition
On the basis of amount part generally preferably in the range of 0.1~20 mass parts, more preferably in the range of 0.3~10 mass parts, enter one
Step is preferably in the range of 0.5~5 mass parts.
In addition, in the case where the coating composition of the present invention uses as pigmented finiss, when containing pigment, pigment
Use level on the basis of the mass parts of solid content 100 in coating composition generally preferably in the range of 1~200 mass parts, more
It is preferred that in the range of 2~100 mass parts, further preferably in the range of 5~50 mass parts.
As above-mentioned ultra-violet absorber, existing known ultra-violet absorber can be used, such as can enumerate：Benzo three
The ultra-violet absorbers such as azoles system absorbent, triazine system absorbent, salicyclic acid derivatives system absorbent, benzophenone series absorbent.
These ultra-violet absorbers can be used alone or be used in combination of two or more.
In the case where the coating composition of the present invention contains ultra-violet absorber, the use level of ultra-violet absorber is to apply
On the basis of the mass parts of solid content 100 in feed composition preferably in the range of 0.1~10 mass parts, more preferably in 0.2~5 matter
In the range of measuring part, further preferably in the range of 0.3~2 mass parts.
As light stabilizer, existing known light stabilizer can be used, such as can enumerate：Amine system of being obstructed light stabilizer.
In the case where the coating composition of the present invention contains light stabilizer, with the matter of solid content 100 in coating composition
On the basis of measuring part, the use level of light stabilizer is preferably in the range of 0.1~10 mass parts, more preferably in 0.2~5 mass parts
In the range of, further preferably in the range of 0.3~2 mass parts.
From the viewpoint of storage stability, coating composition of the invention is preferably made by above-mentioned host and above-mentioned solidification
The two-liquid type coating that agent is formed, use will mix both before use.
In the present invention, aforementioned coating composition can be coated on to plastic basis material face and obtains coated article.As plastics
Base material, it is not particularly limited, such as can enumerates：Polyolefin-based resins representated by polyethylene, polypropylene etc.；Poly- terephthaldehyde
Sour glycol ester resin, polybutylene terephthalate (PBT) (PBT) resin, makrolon (PC) resin, makrolon-poly- to benzene
The thermoplastic polyesters such as dioctyl phthalate butanediol ester (PC/PBT) resin；Acrylonitrile-styrene resin, acrylonitrile-butadiene-benzene
The phenylethylene resin series such as ethene (ABS) resin, acrylonitrile-styrene-acrylic ester (ASA) resin；Other polymethylacrylic acid
Late resin, acrylic resin, vinylidene chloride, polyamide, polyphenylene oxide resin, acetal resin, polyurethane resin, ring
The raw material of oxygen tree fat etc. or their hybrid resin and fibre reinforced plastics (Fiber-Reinforced Plastics) etc.
Face.These former material charge levels can suitably carry out ungrease treatment or surface treatment as needed.And then can also be in plastic basis material face
The coating composition of the application present invention after formation primary coat film.
It is not particularly limited for the method for the coating composition of the application present invention.Such as air-atomizing, nothing can be passed through
Gas blowout mist, rotary-atomizing coating machine, dipping coating, bristle etc. carry out application.
The film formed using the coating composition of the present invention generally generally can be in 3~100 μ with cured film thickness gauge
In the range of m, preferably in the range of 3~50 μm.
For the present invention coating composition coating film-forming methods in heating condition be not particularly limited, can by
50~100 DEG C, preferably keep carry out at 50~90 DEG C within 10~90 minutes.On causing plastic material with deformation because of thermal conductivity
When heating condition, such as kept for 10 minutes~90 minutes preferably at 50 DEG C~80 DEG C in the case of using ABS resin etc..
From marresistance, hardness, outward appearance, tack and patience relative to the composition containing ultra-violet absorber etc. etc.
Viewpoint considers that the glass transition temperature of the cured coating film of the film obtained by the coating composition of the present invention is 20~60
DEG C, be preferably 30~55 DEG C, more preferably 35~50 DEG C for be adapted to.On above-mentioned glass transition temperature, to use
Measurement of Dynamic Viscoelasticity device, bar is prepared into using by the film for 25 μm of thickness for having carried out being heating and curing for 30 minutes at 80 DEG C
Sample obtained from the free film (0.5cm × 2cm) of shape is as measure sample, in 3 DEG C/min of programming rate, temperature range 20
~200 DEG C, when tan δ values are determined under conditions of frequency 11Hz, temperature during tan δ value display maximum.As Dynamic Viscoelastic
Property measure device, FT レ オ ス ペ Network ト ラ DVE-V4 (trade name, レ オ ロ ジ companies manufacture) can be used.
Embodiment
Hereinafter, embodiment and comparative example is enumerated further specifically to illustrate the present invention.But the present invention and not only
It is limited to these embodiments.It should be noted that " part " and " % " represents " mass parts " and " quality % " respectively.In addition, film
Thickness is based on cured coating film.
[manufacture of hydroxy acryl acid resin (A1)]
Production Example 1
Load 50 parts in the reaction vessel for possessing agitating device, thermometer, reflux condenser, thermostat and dropwise addition pump
Butyl acetate, nitrogen is blown into while being warming up to 115 DEG C.Then, 115 DEG C ± 3 DEG C of shape is maintained in by reaction system
Under state, stir while utilizing dropwise addition pump to be added dropwise with 3 hours with certain speed by 25 parts of acrylic acid into reaction vessel
4- hydroxybutyls, 10 parts of acrylic acid 2- hydroxy methacrylates, 25 parts of n-BMA, 40 parts of acrylic acid 2- ethyl hexyls
Ester and the 2 of 2.0 parts, the monomer and the mixture of polymerization initiator that 2 '-azobis isobutyronitrile is formed, then in synthermal lower curing 1
Hour.Then, the 2 of 0.5 part then with 1 hour are added dropwise into reaction vessel, 2 '-azobis isobutyronitrile and 17 parts of butyl acetate
Mixture, after completion of dropwise addition, cure 1 hour, terminate reaction.
The solution of obtained hydroxy acryl acid resin (A1-1) is the uniform clear solution that solid content is 60%.Separately
Outside, the weight average molecular weight of acrylic resin be about 20,000, hydroxyl value 146mgKOH/g, glass transition temperature be -41 DEG C.
Production Example 2~11
Except in above-mentioned Production Example 1, the mixture of monomer being set to beyond being combined into matching somebody with somebody shown in table 1, carries out and makes
The same operation of example 1 is made, obtains hydroxy acryl acid resin (A1-2)~(A1-11) solution that solid content is 60%.It will obtain
The weight average molecular weight of each hydroxy acryl acid resin, hydroxyl value, glass transition temperature be shown in table 1 in the lump.
[manufacture of hydroxy acryl acid resin (A2)]
Production Example 12
Load 60 parts in the reaction vessel for possessing agitating device, thermometer, reflux condenser, thermostat and dropwise addition pump
Butyl acetate, be blown into nitrogen while being stirred at 125 DEG C ± 3 DEG C, 45 parts be added dropwise thereto with certain speed with 3 hours
Methyl methacrylate, 25 parts of acrylic acid 2- hydroxy methacrylates, 20 parts of n-butyl acrylate, 10 parts of the methacrylic acid moon
Osmanthus base ester, the 2 of 2.0 parts, the mixture of 2 '-azobis isobutyronitrile, then in synthermal lower curing 1 hour.Then, then with 1 hour
The mixture of the 2 of 0.5 part of dropwise addition into reaction vessel, 2 '-azobis isobutyronitrile and 21 parts of butyl acetate, after completion of dropwise addition,
Curing 1 hour, terminate reaction.
Obtained hydroxy acryl acid resin (A2-1) solution is the uniform clear solution that solid content is 55%.In addition,
The weight average molecular weight of acrylic resin is about 21,000, hydroxyl value 121mgKOH/g, glass transition temperature are -7 DEG C.
Production Example 13~27
Except in above-mentioned Production Example 12, the mixture of monomer being set to beyond being combined into matching somebody with somebody shown in table 2, carries out and makes
The same operation of example 12 is made, obtains hydroxy acryl acid resin (A2-2)~(A2-16) solution that solid content is 60%.It will obtain
The weight average molecular weight of each hydroxy acryl acid resin, hydroxyl value, glass transition temperature be shown in table 2 in the lump.
[manufacture of hydroxyl group containing polyester resin]
Production Example 28
Load 136 parts of hexahydro neighbour's benzene in the reaction vessel for being equipped with mixer, thermometer, rectifying column and separator
Dicarboxylic acid anhydride, 83 parts of 1,6- hexylene glycols and the three of 78 parts (2- hydroxyethyls) isocyanuric acid esters, are warming up under nitrogen atmosphere
160℃。
Then, 220 DEG C were warming up to 3 hours, add dimethylbenzene, water is distilled off while carrying out under reflux anti-
Should.After being cooled down when as desired acid number, then it is diluted with butyl acetate, obtains the polyester resin that solid content is 50%
(C-1) solution.The number-average molecular weight of the polyester resin (C-1) is 2,200, hydroxyl value 113mgKOH/g.
Production Example 29~31
Except in above-mentioned Production Example 28, the mixture of monomer and polymerization initiator being set to be combined into matching somebody with somebody shown in table 3
In addition, progress and the same operation of Production Example 28, hydroxyl group containing polyester resin (C2-2)~(C2-4) that solid content is 50% is obtained
Solution.The number-average molecular weight of obtained each hydroxyl group containing polyester resin, hydroxyl value are shown in table 3 in the lump.
[manufacture of coating composition]
Embodiment and comparative example
Each composition is equably mixed in a manner of being combined into as matching somebody with somebody shown in table 4.Then, add in obtained mixture
Add retarder thinner, obtain the coating composition that the viscosity using Ford cup No.4 measure at 20 DEG C is 25 seconds.
By as, with composition (A) and composition (C) is mixed in a manner of being combined into, making solid content is about shown in table 4
For 40% each host.By as shown in table 4 with the curing agent that adds composition (B) in a manner of being combined into the host and equal
Mix evenly.Then, retarder thinner is added in obtained mixture, obtains utilizing the viscous of Ford cup No.4 measure at 20 DEG C
Spend the coating composition for 25 seconds.
In addition, table 4 represents for solid content, (B-1)~(B-3) in table 4 is as described below.
(B-1)：デ ュ ラ ネ ー ト 24A-90E, trade name, the manufacture of chemical company of Asahi Chemical Industry, hexamethylene diisocyanate
Biuret form, solid content 90%, NCO containing ratio 21.2%
(B-2)XP2580：Trade name, the manufacture of Bayer companies, the allophanic acid ester type of hexamethylene diisocyanate, Gu
Shape thing 100%, NCO containing ratio 19.5%
(B-3)スミジュールN3300：Trade name, the manufacture of Sumitomo Bayer Urethane companies, hexa-methylene two are different
The urea acid esters body of cyanate, solid content 100%, NCO containing ratio 21.8%
[making of experiment coated plate]
Air-atomizing application is as above made in a manner of solidifying thickness and be about 25 μm on ABS plates (black, through ungrease treatment)
Each coating composition made, being heated 30 minutes at 80 DEG C makes its solidification, obtains each experiment coated plate.
By obtained each experiment coated plate for following performance tests.Result is shown in table 4 in the lump.
[film performance experiment]
Marresistance：Learning vibration shape friction strong testing machine " RT-200 " (trade name, Daiei chemistry Jing Ji manufacturing companies
Manufacture) in the experiment coated plate that as above obtains is set.No.2000 sand paper is attached with two-sided tape on brake pad, in brake pad
Upper mounting 200g weight, it is reciprocal to grind 2 times, film is caused to damage.After standing 24 hours at 25 DEG C, film is determined
L15 ° of value, by and cause the difference (L15 ° of Δ) of L15 ° of value of the film before damage to be evaluated by following benchmark.
On the measure of L15 ° of value, read using multi-angle color difference meter " MA68II " (trade name, X-rite companies manufacture)
Relative to light, vertically (being vertical direction relative to damage) incident direction, acceptance angle are the L values in 15 degree of directions (by it
Referred to as L15 ° value), calculate L15 ° front and rear of difference Δ of experiment.The L15 ° of situation more than 30 of Δ is unqualified.
Pencil hardness：Implement according to JIS K 5600-5-4 (1999).Using the coated surface relative to each experiment coated plate as about
45 ° of angle contacts pencil-lead with coated surface, while pressing on coated surface energetically under the degree that core will not fracture, on one side
Pencil is moved into about 10mm with uniform speed forwards.The operation change position is repeated 5 times, the trace of pencil-lead will not applied
Mark is set to pencil hardness in the hardness mark of the most hard pencil of film.
Tack：Line of cut, system are cut to the coated surface of each experiment coated plate using cutting machine in the way of bed material is reached
Make 100 size 2mm × 2mm grid.Then, cellophane adhesive tape and cloth adhesive tape are bonded in the coated surface, 20
After it is sharp peeled off at DEG C, the number for the grid that investigation film is remained, evaluated by following benchmark.
◎：The number for the grid that film is remained is 100 and by cloth adhesive tape when cellophane adhesive tape is peeled off
The number for the grid that film is remained is 100 during stripping
○：The number for the grid that film is remained is 100 and by cloth adhesive tape when cellophane adhesive tape is peeled off
The number for the grid that film is remained is less than 99 during stripping
×：The number for the grid that film is remained is less than 99 and bonds cloth when cellophane adhesive tape is peeled off
The number for the grid that film is remained is less than 99 when adhesive tape is peeled off
Relative to the patience of the composition containing ultra-violet absorber etc.：It is each experiment coated plate coated surface coating relative to
Unit coating area is 0.5g/100cm2Cosmetics (Givenchy DW UV Shield, trade name, Parfums
The manufacture of Givenchy companies, SPF50PA+++), after being placed 4 hours at 55 DEG C, room temperature is cooled to, wipes the cosmetics on surface,
Evaluate appearance of film, pencil hardness and tack.The measure of pencil hardness is carried out by the method same with the above method, by lead
Hardness mark is from above-mentioned " pencil hardness：" item in obtained hardness mark situation about declining within 2 grades be set to close
Lattice.The evaluation of tack in the same manner as the above method by carrying out.Appearance of film is evaluated by following benchmark.
○：Without abnormal
×：Produce diminution, discoloration, vestige, stripping
The present invention is described in detail by with reference to specific embodiment, but it should be apparent to those skilled in the art that can not taken off
Made various changes and modifications in the case of from the spirit and scope of the present invention.The application is based on filed in September in 2013 10 days
Japanese patent application (Japanese Patent Application 2013-187105), its content are incorporated herein by reference.
Claims (6)
1. a kind of coating composition, it is the Coating material composition of the curing agent comprising host and containing polyisocyanate compound (B)
Thing, the host contain hydroxy acryl acid resin (A), wherein,
The hydroxy acryl acid resin (A) is contained on the basis of the resin solid quality in host
The hydroxyl value of 25 to 95 mass parts is the hydroxy acryl acid that 70 to 200mgKOH/g, glass transition temperature is less than -30 DEG C
Resin (A1), and
The hydroxy acryl acid that the hydroxyl value of 5 to 75 mass parts is 30 to 200mgKOH/g, glass transition temperature is -30~75 DEG C
Resin (A2),
And
The hydroxy acryl acid resin (A2) is on the basis of polymerism unsaturated monomer (a2-1)~(a2-3) total amount, is made
30 to 80 quality % methyl methacrylate (a2-1), 10 to 35 quality % hydroxyl polymerism unsaturated monomer (a2-
2) and 0 to 60 quality % other polymerism unsaturated monomers (a2-3) reaction obtained from hydroxy acryl acid resin.
2. coating composition according to claim 1, wherein, the hydroxy acryl acid resin (A1) be with polymerism not
On the basis of saturation monomer (a1-1) and (a1-2) total amount, make 10 to the 60 quality % hydroxy alkyl with carbon number 4 to 9
Polymerism unsaturated monomer (a1-1) and 40 to 90 quality % other polymerism unsaturated monomers (a1-2) reaction and obtain
Hydroxy acryl acid resin.
3. coating composition according to claim 1 or 2, wherein, the polyisocyanate compound (B) is selected from by contracting
At least one of group that the polyisocyanate compound of two urea types and the polyisocyanate compound of allophanic acid ester type are formed.
4. coating composition according to claim 1 or 2, wherein, the host also contains hydroxyl group containing polyester resin (C).
A kind of 5. coating process, wherein the application coating group according to any one of claim 1 to 4 on plastic basis material face
Compound.
6. a kind of coated article, it is by the application painting according to any one of claim 1 to 4 on plastic basis material face
Obtained from feed composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013187105 | 2013-09-10 | ||
| JP2013-187105 | 2013-09-10 | ||
| PCT/JP2014/063892 WO2015037280A1 (en) | 2013-09-10 | 2014-05-26 | Coating material composition and coated article |
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| Publication Number | Publication Date |
|---|---|
| CN105612227A CN105612227A (en) | 2016-05-25 |
| CN105612227B true CN105612227B (en) | 2017-11-24 |
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| CN201480049961.XA Active CN105612227B (en) | 2013-09-10 | 2014-05-26 | Coating composition and coated article |
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| Country | Link |
|---|---|
| JP (1) | JP5692482B1 (en) |
| CN (1) | CN105612227B (en) |
| WO (1) | WO2015037280A1 (en) |
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| EP3368620B1 (en) * | 2015-10-28 | 2022-03-23 | Swimc LLC | Polyurethane coating composition |
| KR101776434B1 (en) * | 2015-12-16 | 2017-09-07 | 현대자동차주식회사 | Method for manufacturing natural material film having multi-layered coating film |
| KR101811515B1 (en) * | 2016-01-22 | 2017-12-22 | 주식회사 케이씨씨 | High glossy paint composition for interial parts |
| JP6859014B2 (en) * | 2016-11-23 | 2021-04-14 | 関西ペイント株式会社 | Multi-layer coating film forming method |
| CN108727955B (en) * | 2017-04-20 | 2021-08-31 | 关西涂料株式会社 | Multi-component water-based primer coating composition and coating method |
| CN109535901B (en) * | 2017-07-25 | 2021-03-02 | 佩特化工(上海)有限公司 | Water impact resistant dark gray conductive primer for electrostatic coating and preparation method thereof |
| KR102039470B1 (en) * | 2017-12-12 | 2019-11-04 | 주식회사 노루비케미칼 | Coating composition for forming scratch-resistant layer having high strength for automobile exterior and method for coating automobile exterior using the same |
| JP7052774B2 (en) * | 2018-06-27 | 2022-04-12 | 荒川化学工業株式会社 | Thermosetting coatings, cured products and films |
| JP2020007423A (en) * | 2018-07-04 | 2020-01-16 | 富士ゼロックス株式会社 | Solution for forming surface protective resin member, solution set for forming surface protective resin member, and surface protective resin member |
| JP2021116374A (en) * | 2020-01-28 | 2021-08-10 | 荒川化学工業株式会社 | Undercoat agent, cured product, and laminate |
| KR102463072B1 (en) * | 2021-01-26 | 2022-11-03 | 주식회사 케이씨씨 | Coating method for providing textured coating |
| CN114854296A (en) * | 2022-04-26 | 2022-08-05 | 河南东澳化工有限公司 | Special coating for ABS (acrylonitrile butadiene styrene) plastics and preparation method thereof |
| WO2024002697A1 (en) | 2022-06-29 | 2024-01-04 | Basf Coatings Gmbh | A 2k clearcoat coating composition |
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| US4565730A (en) * | 1983-06-18 | 1986-01-21 | Basf Farben & Fasern Ag | Coating composition, in particular for producing a transparent topcoat of a multilayer coating, a process for producing coatings, and an article coated with a multilayer coating |
| US6294607B1 (en) * | 1999-09-08 | 2001-09-25 | Arco Chemical Technology, L.P. | Ultra-high-solids acrylic coatings |
| CN101784623A (en) * | 2007-08-22 | 2010-07-21 | 巴斯福涂料股份有限公司 | Paint compositions, a method of finish-painting and painted objects |
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| US3998768A (en) * | 1974-12-24 | 1976-12-21 | E. I. Du Pont De Nemours And Company | Thermosetting powder coating composition of a blend of acrylic polymers having different glass transition temperatures and a blocked polyisocyanate cross-linking agent |
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| EP0885908A1 (en) * | 1997-06-19 | 1998-12-23 | Basf Corporation | Coating composition based on a polyacrylate resin containing hydroxyl groups, and its use in processes for the production of coatings |
| US6472493B1 (en) * | 1999-11-23 | 2002-10-29 | E. I. Du Pont De Nemours And Company | Clear coating composition having improved early hardness and water resistance |
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| JP5074022B2 (en) * | 2006-12-28 | 2012-11-14 | 関西ペイント株式会社 | Base coating composition and coating composition containing the same |
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- 2014-05-26 WO PCT/JP2014/063892 patent/WO2015037280A1/en active Application Filing
- 2014-05-26 JP JP2014550955A patent/JP5692482B1/en active Active
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| US4565730A (en) * | 1983-06-18 | 1986-01-21 | Basf Farben & Fasern Ag | Coating composition, in particular for producing a transparent topcoat of a multilayer coating, a process for producing coatings, and an article coated with a multilayer coating |
| US6294607B1 (en) * | 1999-09-08 | 2001-09-25 | Arco Chemical Technology, L.P. | Ultra-high-solids acrylic coatings |
| CN101784623A (en) * | 2007-08-22 | 2010-07-21 | 巴斯福涂料股份有限公司 | Paint compositions, a method of finish-painting and painted objects |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105612227A (en) | 2016-05-25 |
| JP5692482B1 (en) | 2015-04-01 |
| JPWO2015037280A1 (en) | 2017-03-02 |
| WO2015037280A1 (en) | 2015-03-19 |
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