CN105658747B - Coating composition and coated article - Google Patents
Coating composition and coated article Download PDFInfo
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- CN105658747B CN105658747B CN201480049628.9A CN201480049628A CN105658747B CN 105658747 B CN105658747 B CN 105658747B CN 201480049628 A CN201480049628 A CN 201480049628A CN 105658747 B CN105658747 B CN 105658747B
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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
- C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/46—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
- C08G18/70—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
- 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
- C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
- C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate 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
- C09D133/062—Copolymers with monomers not covered by C09D133/06
- C09D133/066—Copolymers with monomers not covered by C09D133/06 containing -OH groups
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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
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
- C09J175/04—Polyurethanes
-
- 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
- C08G2101/00—Manufacture of cellular products
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Paints Or Removers (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
It is an object of the invention to provide a kind of coating composition and coated article of the film for being formed and having excellent marresistance, hardness, outward appearance, tack and chemical-resistant relative to plastic basis material.The coating composition of the present invention includes the host containing specific hydroxy acryl acid resin (A) and specific hydroxyl group containing polyester resin (B) and the curing agent containing specific polyisocyanate compound (C), and the glass transition temperature of obtained film is 20 to 60 DEG C.
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, communication equipment, family's electrical article, automobile with having used ABS resin in the various industrial products such as part, it is poly-
The plastic basis materials such as propylene, polyurethane resin, polycarbonate resin.Require the industrial product marresistance, it is hardness, outward appearance, attached
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 the industrial product for forming multilayer film, its
In, also require full in the once coating process of baking (application is once sintered) is once coated with using a kind of coating
The industrial product of sufficient tack and various film performances, is used as problem, it is desirable to is once coated with and once toasts more difficult.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 as the cosmetics such as frost is even in being attached to painting
Placed in the state of film surface will not also occur film attachment is bad, outward appearance reduction and hardness reduction etc. (it is following, be slightly designated as sometimes
" for the patience of the composition containing ultra-violet absorber etc. ").
For example in patent document 1, as the coating that traumatic resistance and acid resistance are excellent, a kind of automotive clear is disclosed
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 used 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, so that from containing internal ester monomer
Ratio of the soft chain segment portion relative to the hydroxy acryl acid resin and the total solid of polyfunctional isocyanate compound
It is that 30~60 DEG C of the mode of scope is entered for below 4.5 mass % and obtained cured coating film dynamic glass transition temperature
It is prepared by row.
However, the coating is primarily adapted for metal base, coating process is once toasted in the once coating relative to 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 that 80~220mgKOH/g, glass transition temperature less than 0 DEG C and contain 25 as -50 DEG C that it, which is,
The hydroxy-containing resin (A) of~55 mass % unit from (methyl) acrylic acid 4- hydroxybutyls, hydroxyl value be 80~
220mgKOH/g, glass transition temperature are 0~50 DEG C of hydroxy-containing resin (B) and are 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 hydroxy-containing resin (A) and total hydroxyl of hydroxy-containing resin (B) content ratio 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 in the once coating relative to 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 [many 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 the equal molecule of number
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 [many 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.
In patent document 6, reviewing one's lessons by oneself that the damage that can form generation on the surface of various base materials disappears in the short time is used as
The coating composition of the film of renaturation, discloses a kind of coating composition, and it contains hydroxyl value for 40~80mgKOH/g and glass
Change transition temperature is -40~-10 DEG C of PEPA (A) and hydroxyl value is 35~65mgKOH/g and glass transition temperature
For 50~70 DEG C of PEPAs (B) and the trimer (C) of aliphatic diisocyanate, and (A) composition and (B) composition
Use weight ratio [(A)/(B)] be 45/55~85/15, and the total mole number (OH) of the hydroxyl of (A) composition and (B) composition and
(C) the ratio between molal quantity (NCO) of the NCO of composition [NCO/OH] is 0.8~2.But, although the coating composition exists
The self-repairability and excellent adhesion being once coated with once baking coating process, but relative to containing ultra-violet absorber etc.
The patience of composition is insufficient.
There is a kind of hardening resin composition towards hot forming film disclosed in patent document 7, 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 with case hardness, the resin combination contains with carboxyl and hydroxyl, consolidated
Shape thing acid number is 15~150mgKOH/g, glass transition temperature is 70~140 DEG C vinyl polymers (A) and many isocyanides
Ester compound (B), the content of polyisocyanate compound (B) be with the solid content hydroxyl values 2 of vinyl polymers (A)~
The content of 80mgKOH/g reactions.But, should once it be toasted being once coated with the hardening resin composition of film towards thermoforming
It is insufficient to the tack and marresistance of ABS plates 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 2012-140614 publications
Patent document 7：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 baking 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.
Technical scheme for solving 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, and the coating composition, which is included, contains specific hydroxy acryl acid
The host of resin and hydroxyl group containing polyester resin and the curing agent containing specific polyisocyanate compound, wherein obtained painting
The glass transition temperature of film is 20~60 DEG C.
That is, the present invention provides article obtained from following coating composition and the application coating composition.
The present invention relates to following (1)~(5).
(1) a kind of coating composition, it is the coating of the curing agent comprising host and containing polyisocyanate compound (C)
Composition, the host contains hydroxy acryl acid resin (A) and hydroxyl group containing polyester resin (B), wherein,
The hydroxyl value of hydroxy acryl acid resin (A) is 100~200mgKOH/g, and glass transition temperature is less than -20 DEG C,
The hydroxy acryl acid resin (A) is on the basis of polymerism unsaturated monomer (a1)~(a3) total amount, to make
15~35 mass % methyl methacrylate (a1), 5~30 mass % hydroxy alkyl with carbon number 4~9 it is poly-
Contain hydroxyl obtained from conjunction property unsaturated monomer (a2) and 35~80 mass % other polymerism unsaturated monomers (a3) reaction
Base acrylic resin,
The hydroxyl value of hydroxyl group containing polyester resin (B) is that 50~200mgKOH/g, number-average molecular weight are 2,000~20,000, and
And the hydroxyl group containing polyester resin (B) be by hydroxyl group containing polyester resin obtained from the reaction of polyalcohol and polyacid, it is described
Polyalcohol includes the cyclic polyol alcoholic compound (b1) with urea acrylate structure (ヌ レ ー ト Agencies make),
Polyisocyanate compound (C) is selected from by biuret-containing Quito isocyanate compound and special allophanates containing base
At least one in the group that polyisocyanate compound is constituted,
The glass transition temperature of obtained film is 20~60 DEG C.
(2) coating composition according to above-mentioned (1), wherein, on the basis of the resin solid quality in host, contain
There are the mass parts of hydroxy acryl acid resin (A) 10~80, the mass parts of hydroxyl group containing polyester resin (B) 20~90.
(3) coating composition according to above-mentioned (1) or (2), wherein, molecular weight is between the crosslinking of obtained film
300~1000.
(4) a kind of coating process, wherein the coating group on plastic basis material any one of application above-mentioned (1)~(3)
Compound.
(5) a kind of coated article, it is by the painting any one of application above-mentioned (1)~(3) on plastic basis material
Obtained from feed composition.
Invention effect
According to the coating composition of the present invention, it can be formed in once baking coating process is once coated with relative to plastics base
Material has excellent marresistance, hardness, outward appearance, tack and had 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 includes host and the curing agent containing polyisocyanate compound (C), and host contains
Hydroxy acryl acid resin (A) and hydroxyl group containing polyester resin (B).
(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) can make methyl methacrylate (a1) as polymerism unsaturated monomer by using conventional method, have
The polymerism unsaturated monomer (a2) of the hydroxy alkyl of carbon number 4~9 and other polymerism unsaturated monomer (a3) copolymerization and
Synthesis.
As the polymerism unsaturated monomer (a2) of the hydroxy alkyl with carbon number 4~9, it can enumerate：(methyl)
Acrylic acid 4- hydroxybutyls, (methyl) acrylic acid 5- hydroxyls pentyl ester, the own ester of (methyl) acrylic acid 6- hydroxyls, (methyl) acrylic acid 7-
Hydroxyl heptyl ester, (methyl) acrylic acid 8- hydroxyls monooctyl ester, (methyl) acrylic acid 7- methyl -8- hydroxyls monooctyl ester, (methyl) acrylic acid 2-
Methyl -8- hydroxyls monooctyl ester, (methyl) acrylic acid 9- hydroxyl nonyl esters etc., these can individually using or be applied in combination 2 kinds with
On.Examined from marresistance, outward appearance, tack and the viewpoint excellent relative to the patience of the composition containing ultra-violet absorber etc.
Consider, as the polymerism unsaturated monomer (a2) of the hydroxy alkyl with carbon number 4~9, wherein particularly preferably (methyl) third
Olefin(e) acid 4- hydroxybutyls, the own ester of (methyl) acrylic acid 6- hydroxyls.
As other polymerism unsaturated monomers (a3), for example, it can enumerate：(methyl) acrylic acid 2- hydroxy methacrylates, (first
Base) acrylic acid 2- hydroxy propyl esters, (methyl) acrylic acid 3- hydroxy propyl esters, polyethyleneglycol (methyl) acrylate, polypropylene glycol
The monoesters compound of the polyalcohols such as (methyl) acrylate and (methyl) acrylic acid, by 6-caprolactone and the polyalcohol and (methyl) third
Compound of monoesters compound ring-opening polymerisation of olefin(e) acid etc. has the polymerism of the hydroxy alkyl of carbon number 4~9 unsaturated
Hydroxyl polymerism unsaturated monomer beyond monomer；
Methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (first
Base) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl)
Hexyl 2-propenoate, 2-EHA, (methyl) cyclohexyl acrylate, (methyl) n-octyl, (methyl) propylene
(the first such as sour nonyl ester, (methyl) lauryl acrylate, (methyl) isobornyl acrylate, (methyl) octadecyl acrylate
Base) acrylic acid Arrcostab；
The unsaturated monomer of polymerism containing carboxyl such as (methyl) acrylic acid, maleic acid, maleic anhydride；
(methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- diethylamino ethyl ester, (methyl)
(methyl) acrylates such as acrylic acid N, N- dimethylamino propyl ester；
Acrylamide, Methacrylamide, N, N- dimethyl aminoethyls (methyl) acrylamide, N, N- diethylaminos
Ethyl (methyl) acrylamide, N, N- dimethylaminopropyls (methyl) acrylamide, N hydroxymethyl acrylamide, N- methylols
Acrylamide methyl ether, N hydroxymethyl acrylamide butyl ether etc. (methyl) acrylamide or derivatives thereof；
2- (methacryloxy) ethyl-trimethyl salmiac, 2- (methacryloxy) ethyMmethylammonium bromide
Deng the monomer containing quaternary ammonium salt base；
(methyl) acrylamide-alkanesulfonic acids such as 2- acrylamide -2- methyl propane sulfonic acids, (methyl) acrylic acid 2- sulfo groups
Ethyl ester etc. (methyl) sulfoethyl Arrcostab；
Acrylonitrile, methacrylonitrile, vinyl acetate, styrene, vinyltoluene, α-methylstyrene etc. contain aromatic rings
Polymerism unsaturated monomer；
Many vinyl compounds such as ALMA；
γ-(methyl) acryloxypropyl trimethoxy silane, γ-(methyl) acryloxypropyl triethoxysilicane
The polymerism containing hydrolyzable silyl group such as alkane, γ-(methyl) acryloxypropyl dimethoxysilane is unsaturated single
Body etc., these can individually using or two or more is applied in combination.
Wherein, from obtaining marresistance, hardness, outward appearance, tack and relative to the combination containing ultra-violet absorber etc.
From the viewpoint of the excellent film of the patience of thing, as other polymerism unsaturated monomers (a3), preferably comprise with carbon atom
Hydroxyl polymerism unsaturated monomer, (methyl) acrylic acid beyond the polymerism unsaturated monomer of the hydroxy alkyl of number 4~9
Arrcostab.
As the hydroxyl polymerism beyond the polymerism unsaturated monomer of the hydroxy alkyl with carbon number 4~9 not
Saturation monomer, particularly preferred (methyl) acrylic acid 2- hydroxy methacrylates.
As the Arrcostab of (methyl) acrylic acid, the carbon number of particularly preferred moieties is 4~8 polymerism insatiable hunger
And monomer, wherein, 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, particularly preferred (methyl) n-butyl acrylate, (methyl) 2-EHA.
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 " refers to acrylamide or Methacrylamide.
From the marresistance of obtained film, hardness, outward appearance, tack and relative to the group containing ultra-violet absorber etc.
Methyl methacrylate (a1) in the consideration of the viewpoints such as the patience of compound, above-mentioned monomer component, the hydroxyl with carbon number 4~9
The polymerism unsaturated monomer (a2) of base alkyl and the use ratio of other polymerism unsaturated monomers (a3) are with monomer component
On the basis of the gross mass of (polymerism unsaturated monomer (a1)~(a3)) in following scopes.
Methyl methacrylate (a1)：15~35 mass %, preferably 20~30 mass %, more preferably 22~27
Quality %；
The polymerism unsaturated monomer (a2) of hydroxy alkyl with carbon number 4~9：5~30 mass %, preferably 10
~25 mass %, more preferably 12~20 mass %；
Other polymerism unsaturated monomers (a3)：35~80 mass %, preferably 45~70 mass %, more preferably
43~66 mass %.
Above-mentioned polymerism unsaturated monomer (a1)~(a3) copolymerization is preferably based on the copolymerization of solution polymerization process, for example may be used
To enumerate：The mixture of polymerism unsaturated monomer and radical polymerization initiator is dissolved or is scattered in organic solvent, lead to
Stirred at a temperature of 80 DEG C of Chang Yue~about 200 DEG C 1~10 hour while heating the method for polymerizeing it.
In the present invention, hydroxy acryl acid resin (A) be hydroxyl value be 100~200mgKOH/g, be preferably 105~
170mgKOH/g, more preferably 110~150mgKOH/g and glass transition temperature less than -20 DEG C, preferably shorter than -23
DEG C, even more preferably below -25 DEG C of hydroxy acryl acid resin.If the hydroxyl value of hydroxy acryl acid resin (A) is
More than 100mgKOH/g, then the patience relative to the composition containing ultra-violet absorber etc. becomes good, if 200mgKOH/
Below g, the then marresistance of the film obtained becomes good, therefore it is preferred that.In addition, if glass transition temperature is more than -20 DEG C,
Sometimes the marresistance of film and hardness are deteriorated.
It should be noted that in this manual, the glass transition temperature Tg of hydroxy acryl acid resin (A) is under
The value that the formula of stating is calculated.
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.Gru lke are compiled (1999 years)
The glass transition temperature for the monomer do not recorded in the value arrived, the document uses following value：The homopolymer of the monomer is equal with weight
The mode that molecular weight is 50,000 or so is synthesized, and value during its glass transition temperature is determined by differential scanning type heat analysis.
In the present invention, from marresistance, hardness, outward appearance, tack and relative to the group containing ultra-violet absorber etc.
Consider in terms of the patience of compound, the weight average molecular weight of hydroxy acryl acid resin (A) is 5,000~33,000, preferably 8,
000~30,000 scope.
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) is measured
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 that eastern Cao (strain) is public
Department's manufacture, trade name) this 4, mobile phase be tetrahydrofuran, to determine temperature be 40 DEG C, flow velocity is 1ml/ minutes, detector is
Carried out under conditions of RI.
In the present invention, the content of hydroxy acryl acid resin (A) is on the basis of total resin solid quality in host
Preferably 10~80 mass parts, more preferably 55~75 mass parts.If above range, then from the scratch resistance of obtained film
Property, the viewpoint such as hardness, outward appearance, tack and the patience relative to the composition containing ultra-violet absorber etc. consider preferred.
<Hydroxyl group containing polyester resin (B)>
Hydroxyl group containing polyester resin (B) can typically make polyalcohol and polyacid in hydroxyl by using its own known method
Esterification is carried out under excessive and is obtained.Polyalcohol is the compound with more than 2 hydroxyls in 1 molecule, and polyacid is 1 molecule
In there is the compounds of more than 2 carboxyls.
In the coating composition of the present invention, hydroxyl group containing polyester resin (B) is included has urea acid esters knot as polyalcohol
The cyclic polyol alcoholic compound (b1) of structure.
As the cyclic polyol alcoholic compound (b1) with urea acrylate structure, for example, it 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, the 6-caprolactone modifier of three (hydroxy alkyl) isocyanuric acid ester, 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 with urea acrylate structure
The hydroxyl of polyisocyanate compound and diol compound in diol compound is relative to many 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 two or more is applied in combination.
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.
As the polyalcohol beyond composition (b1), for example, it can enumerate：Ethylene glycol, propane diols, diethylene glycol, trimethylene
Glycol, tetraethylene glycol, triethylene glycol, DPG, 1,4- butanediols, 1,3 butylene glycol, 2,3- butanediols, 1,2- butanediols,
3- methyl isophthalic acids, 2- butanediols, 1,2- pentanediols, 1,5- pentanediols, 1,4- pentanediols, 2,4-PD, 2,3- dimethyl Sanya
Methyl glycol, tetramethylene glycol, 3- methyl -4,3- pentanediols, 3- methyl -4,5- pentanediols, 2,2,4- trimethyls -1,3- penta
Glycol, 1,6-HD, 1,5- hexylene glycols, 1,4- hexylene glycols, 2,5-HD, neopentyl glycol, 3-hydroxypivalic acid neopentyl glycol
The dihydric alcohols such as ester；By the addition of the lactone such as 6-caprolactone in the polylactone diol of these 2 yuan of alcohol；Double (the hydroxyls of terephthalic acid (TPA)
Base ethyl) the esterdiol class such as ester；The polyethers such as alkylene oxide adducts, polyethylene glycol, polypropylene glycol, the polytetramethylene glycol of bisphenol-A two
Alcohols；The alpha-olefin epoxides, カ ー ジ ュ ラ such as expoxy propane and epoxy butane E10 [manufacture of シ ェ Le chemical company, commodity
Name, synthesis highly -branched saturated fatty acid ethylene oxidic ester] etc. mono-epoxy compounds；Glycerine, trimethylolpropane, trihydroxy methyl
More than 3 yuan of ethane, two glycerine, triglycerin, 1,2,6- hexanetriols, pentaerythrite, dipentaerythritol, sorbierite, mannitol etc.
Alcohol；By the addition of the lactone such as 6-caprolactone in the poly-lactone polyol class of these more than 3 yuan of alcohol；1,4- hexamethylene diformazans
Alicyclic polyols such as alcohol, Tricyclodecane Dimethanol, hydrogenated bisphenol A, A Hydrogenated Bisphenol A F, hydrogenated bisphenol A and A Hydrogenated Bisphenol A F etc..
It is above-mentioned to contain hydroxyl from the aspect of patience of the obtained film relative to the composition containing ultra-violet absorber etc.
The content ratio of the cyclic polyol alcoholic compound (b1) with urea acrylate structure in base polyester resin (B) is with the total amount of alcohol composition
On the basis of, preferably in the range of 1~75mol%, more preferably in the range of 10~60mol%.If with urea acrylate structure
Cyclic polyol alcoholic compound (b1) content ratio be above range, then relative to the composition containing ultra-violet absorber etc.
Patience become good.
Polyacid can for example be enumerated：Terephthalic acid (TPA), M-phthalic acid, phthalic acid, naphthalene dicarboxylic acids, 4,4 '-connection
Benzene dicarboxylic acid, diphenyl methane -4,4 ' aromatic polyvalent such as-dicarboxylic acids acid and its acid anhydrides；Hexahydro M-phthalic acid, hexahydro are to benzene
The alicyclic dicarboxylic acids such as dioctyl phthalate, hexahydrophthalic acid, tetrahydrophthalic acid and its acid anhydrides；Adipic acid, decanedioic acid, pungent two
Acid, butanedioic acid, glutaric acid, maleic acid, chloromaleic acid, fumaric acid, dodecanedioic acid, pimelic acid, azelaic acid, itaconic acid, lemon
Aliphatic polybasic acids and its acid anhydrides such as health acid, dimeric dibasic acid；The lower alkyl esters such as methyl esters, the ethyl ester of these dicarboxylic acids；Trimellitic acid,
Trimellitic anhydride, pyromellitic acid, pyromellitic dianhydride, trimesic acid, methylcyclohexene tricarboxylic acids, tetrachloro hexene polyacid and its
Polyacid that more than 3 yuan of acid anhydrides etc. 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, for example, it can enumerate：Benzoic acid or t-butyl perbenzoate etc., as oil into
Point, it can such as 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 the hydroxyl value of hydroxyl group containing polyester resin (B) is 50~200mgKOH/g, preferably
For 50~150gKOH/g, number-average molecular weight is 2,000~20,000, is preferably 2,000~15,000.
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 (B) is preferably 20 on the basis of the total solid in host
The scope of~90 mass parts, more preferably 25~45 mass parts.
The host of the present invention using hydroxy acryl acid resin (A) and hydroxyl group containing polyester resin (B) as must composition, can be with
Further as needed containing resin components such as hydroxyl polyurethane resin, phenolic resin, polycarbonate resin and epoxy resin.
(curing agent)
Curing agent used in the present invention contains polyisocyanate compound (C).
<Polyisocyanate compound (C)>
Polyisocyanate compound (C), which contains, to be selected from by special allophanates containing Quito isocyanate compound and biuret-containing
At least one in the group that Quito isocyanate compound is constituted is used as required composition.
Above-mentioned special allophanates containing Quito isocyanate compound is to make to be selected from many isocyanides of aliphatic by known method
Polyisocyanates in acid esters, alicyclic polyisocyanates and aromatic polyisocyanate etc. carry out allophanatization reaction and
Obtained compound.
Above-mentioned biuret-containing Quito isocyanate compound be by known method make selected from aliphatic polyisocyante,
Polyisocyanates in alicyclic polyisocyanates and aromatic polyisocyanate etc. change obtained from biuretized reaction
Compound.
As above-mentioned aliphatic polyisocyante, it can enumerate：Diisocyanate (such as trimethylene diisocyanate,
1,2- trimethylene diisocyanates, tetramethylene diisocyanate, 1,2- tetramethylene diisocyanates, the isocyanide of 2,3- butylidenes two
Acid esters, 1,3- tetramethylene diisocyanates, hexamethylene diisocyanate, pentamethylene diisocyanate, 2,4,4- or 2,2,
The C2-16 such as 4- trimethyl hexamethylene diisocyanates alkane diisocyanates, the isocyanatomethyl capronates of 2,6- bis-
Deng), polyisocyanates (such as lysine ester triisocyanate, the isocyanato- octanes of 1,4,8- tri-, the isocyanic acids of 1,6,11- tri-
Root closes hendecane, the isocyanato- -4- isocyanatomethyls octanes of 1,8- bis-, the isocyanato- hexanes of 1,3,6- tri-, 2,5,
C6-20 alkane triisocyanates such as the isocyanato- -5- isocyanatomethyl octanes of 7- trimethyls -1,8- two etc.) etc..
As above-mentioned alicyclic polyisocyanates, it can enumerate：Diisocyanate is (for example, the isocyanic acid of 1,3- pentamethylene two
Ester, 1,4- cyclohexane diisocyanates, 1,3- cyclohexane diisocyanates, 3- isocyanatomethyl -3,5,5- front three basic rings
Hexyl isocyanates (trivial name：IPDI), 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), methyl -2,
Double (isocyanatomethyl) hexamethylenes of 4- cyclohexane diisocyanates, methyl -2,6- cyclohexane diisocyanates, 1,3- or 1,4-
Alkane (trivial name：Hydrogenated xylylene diisocyanate) or its mixture, norbornene alkyl diisocyanate etc.), many isocyanides
Acid esters is (for example, 1,3,5- tri- isocyanatocyclohexane, 1,3,5- trimethyl isocyanatocyclohexanes, 2- (3- isocyanos
Closing propyl group) -2,5- two (isocyanatomethyl)-bicyclic [2.2.1] heptane, 2- (3- isocyanatopropyls) -2,6- two be (different
Cyanate radical closes methyl)-bicyclic [2.2.1] heptane, 3- (3- isocyanatopropyls) -2,5- two (isocyanatomethyl)-bis-
Ring [2.2.1] heptane, 5- (2- isocyanatoethyls) -2- isocyanatomethyls -3- (3- isocyanatopropyls)-bicyclic
[2.2.1] heptane, 6- (2- isocyanatoethyls) -2- isocyanatomethyls -3- (3- isocyanatopropyls)-bicyclic
[2.2.1] heptane, 5- (2- isocyanatoethyls) -2- isocyanatomethyls -2- (3- isocyanatopropyls)-bicyclic
[2.2.1]-heptane, 6- (2- isocyanatoethyls) -2- isocyanatomethyls -2- (3- isocyanatopropyls)-bicyclic
Triisocyanates such as [2.2.1] heptane etc.).
As above-mentioned aromatic polyisocyanate, it can enumerate：Diisocyanate is (for example, 1,3- or Isosorbide-5-Nitrae-xyxylene
Diisocyanate or its mixture, ω, double (the 1- isocyanic acids of the isocyanato- -1,4- of ω '-two diethylbenzenes, 1,3- or 1,4-
Root conjunction -1- Methylethyls) benzene (trivial name：Tetramethyl xylylene diisocyanate) or its mixture, metaphenylene two it is different
Cyanate, to phenylene vulcabond, 4,4 '-methyl diphenylene diisocyanate, 1,5- naphthalene diisocyanates, 2,4 '-or
4,4 '-methyl diphenylene diisocyanate or its mixture, 2,4- or 2,6- toluene di-isocyanate(TDI)s or its mixture, 4,
4 '-toluidine diisocyanate, 4,4 '-diphenyl ether diisocyanate etc.), polyisocyanates is (for example, 1,3,5- tri- isocyanic acid
Root closes triisocyanate, the triphenyl methanes -4,4 such as methylbenzene ', 4 "-triisocyanate, the isocyanato- benzene of 1,3,5- tri-, 2,
Triisocyanate, such as 4,4 '-diphenyl methanes -2,2 such as the isocyanato- toluene of 4,6- tri- ', 5,5 '-tetraisocyanate etc. four
Isocyanates etc.).
Wherein, from the marresistance of obtained film, hardness, outward appearance, tack and relative to containing ultra-violet absorber
Deng composition patience in terms of consider, can particularly preferably use aliphatic polyisocyante biuret-containing Quito isocyanic acid
Ester compounds or special allophanates containing Quito isocyanate compound.
In above-mentioned aliphatic polyisocyante, from the marresistance of obtained film, hardness, outward appearance, tack and relative
Consider in terms of the patience of the composition containing ultra-violet absorber etc., can particularly preferably use the isocyanic acid of hexa-methylene two
Ester.
Polyisocyanate compound (C) can contain above-mentioned special allophanates containing Quito isocyanate compound as needed
And/or the polyisocyanate compound beyond the isocyanate compound of biuret-containing Quito.
It can such as enumerate：Hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, the isocyanide of dimeric dibasic acid two
The aliphatic polyisocyante class such as acid esters, lysine diisocyanate；The isocyanurate ring of these aliphatic polyisocyantes
Addition product, urea diketone type addition product；IPDI, 4,4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), methyl ring
The alicyclic diisocyanate class such as hexane -2,4- or -2,6- diisocyanate；The isocyanide urea of these alicyclic diisocyanates
Acid esters cycloaddition thing；Xylylene diisocyanate, tetramethyl xylylene diisocyanate, toluene di-isocyanate(TDI), 4,4 '-
The aromatic diisocyanates such as methyl diphenylene diisocyanate (MDI), 1,5- naphthalene diisocyanates, 1,4- naphthalene diisocyanates
Compound；The isocyanurate ring addition product of these aromatic diisocyanates；Hydrogenate MDI and hydrogenate MDI derivative；Make second
The polyalcohols such as glycol, propane diols, 1,4- butanediols, dihydromethyl propionic acid, PAG, trimethylolpropane, hexanetriol
The polyurethane-reinforcement addition product that is reacted with the excessive ratio of NCO with polyisocyanate compound of hydroxyl；These gather
Isocyanurate ring addition product of urethane addition product etc..
On above-mentioned polyisocyanate compound (C) 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,
Coating used in the generally 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 usable hydrocarbon system, ester system, ether system, alcohol system, ketone system generally
Paint solvent.
As above-mentioned curing catalysts, for example, it 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 be further as needed and with 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, for example, it 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 pigment 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, which can be used alone or combine, to be made
Use two or more.
In the case where the coating composition of the present invention is used 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 is used as pigmented finiss, when containing pigment, pigment
Use level is generally preferable in the range of 1~200 mass parts on the basis of the mass parts of solid content 100 in coating composition, 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, for example, 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 two or more is applied in combination.
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 amount part, further preferably in the range of 0.3~2 mass parts.
As light stabilizer, existing known light stabilizer can be used, for example, can enumerate：Amine system of being obstructed light stabilizer.
In the case where the coating composition of the present invention contains light stabilizer, the use level of light stabilizer is with antiglossing pigment group
On the basis of the mass parts of solid content 100 in compound 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.
In the present invention, aforementioned coating composition can be coated on to plastic basis material face and obtains coated article.It is used as plastics
Base material, is not particularly limited, for example, can enumerate：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
Form the coating composition of the application present invention after primary coat film.
The method of the coating composition of the application present invention is not particularly limited.For example can be by air-atomizing, without 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 is usual to solidify typically 3~100 μm of film thickness gauge,
It is preferred that can be in the range of 3~50 μm.
Heating condition in the coating film-forming methods of the coating composition of the present invention is not particularly limited, can by 50~
100 DEG C, preferably keep carrying out for 10~90 minutes at 50~90 DEG C.On because thermal conductivity cause plastic material with deformation when
Heating condition, is kept for 10 minutes~90 minutes such as in the case of using ABS resin preferably at 50 DEG C~80 DEG C.
From marresistance, hardness, outward appearance, tack and patience relative to the composition containing ultra-violet absorber etc. etc.
From the aspect of, 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, preferably 30~55 DEG C, more preferably 35~50 DEG C.On above-mentioned glass transition temperature, to use Dynamic Viscoelastic
Property determine device, prepare into strips free using by the film of 25 μm of thickness for having carried out being heating and curing for 30 minutes at 80 DEG C
Sample obtained from film (0.5cm × 2cm) as determine sample, 3 DEG C/min of programming rate, temperature range -25~100 DEG C,
When determining tan δ values under conditions of frequency 11Hz, temperature during tan δ value display maximum.Filled as Measurement of Dynamic Viscoelasticity
Put, FT レ オ ス ペ Network ト ラ DVE-V4 (trade name, the manufacture of レ オ ロ ジ companies) can be used.
From marresistance, hardness, outward appearance, tack and patience relative to the composition containing ultra-violet absorber etc. etc.
From the aspect of, between the crosslinking after the solidification of film obtained by the coating composition of the present invention molecular weight be preferably 300~
1000, more preferably 350~900, more preferably 400~800.Molecular weight is that will pass through above-mentioned method between above-mentioned crosslinking
The theory that the value of the glass transition temperature of the film measured substitutes into Flory etc. following rubber Theory of Viscoelasticity formula and tried to achieve
Calculated value.
Molecular weight (Mc)=3 ρ RT/E between crosslinkingmin
[in formula, EminThe storage elastic modulus (dyne/cm) in rubber areas is represented, ρ represents the proportion (g/ of coated film of sample
cm3), R is gas constant, R=8.31 × 107(erg/degmol), T represents that storage elastic modulus is EminWhen absolute temperature
Degree.]
Embodiment
Hereinafter, embodiment and comparative example is enumerated further specifically to illustrate the present invention.But, the present invention and not only
It is defined in these embodiments.It should be noted that " part " and " % " represents " mass parts " and " quality % " respectively.In addition, film
Thickness be based on cured coating film.
[manufacture of hydroxy acryl acid resin (A)]
Production Example 1
Load acetic acid in the reaction vessel for possessing agitating device, thermometer, reflux condenser, thermostat and dropwise addition pump
60 parts of butyl ester, is blown into nitrogen while being stirred at 125 DEG C ± 3 DEG C, methyl-prop was added dropwise thereto with certain speed with 3 hours
26 parts of e pioic acid methyl ester, 14 parts of acrylic acid 4- hydroxybutyls, 24 parts of n-butyl acrylate, 24 parts of 2-EHA, propylene
12 parts of sour 2- hydroxy methacrylates and 2, the mixture that 2.0 parts of 2 '-azobis isobutyronitrile, then in synthermal lower curing 1 hour.Then,
Again with the mixture that 21 parts of 0.5 part of 2,2 '-azobis isobutyronitrile and butyl acetate is added dropwise for 1 hour into reaction vessel, knot is added dropwise
Shu Hou, is cured 1 hour, terminates reaction.
Obtained hydroxy acryl acid resin (A-1) solution is the uniform clear solution that solid content is 55%.In addition, third
The weight average molecular weight of olefin(e) acid resin be about 21,000, hydroxyl value be 113mgKOH/g, glass transition point temperature be -29 DEG C.
Production Example 2~19
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, carried out and system
The same operation of example 1 is made, hydroxy acryl acid resin (A-2)~(A-19) solution that solid content is 55% is obtained.By what is obtained
The weight average molecular weight of each hydroxy acryl acid resin, hydroxyl value, glass transition temperature are shown in table 1 in the lump.
[table 1]
[table 2]
[manufacture of hydroxyl group containing polyester resin (B)]
Production Example 20
Load hexahydrophthalic acid in the reaction vessel for being equipped with mixer, thermometer, rectifying column and separator
136 parts of acid anhydride, 83 parts of 1,6- hexylene glycols and three 78 parts of (2- hydroxyethyls) isocyanuric acid esters, are warming up to 160 DEG C under nitrogen atmosphere.
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%
(B-1) solution.The number-average molecular weight of the polyester resin (B-1) is 2,200, and hydroxyl value is 106mgKOH/g.
Production Example 21~28
Except in above-mentioned Production Example 20, the mixture of monomer and polymerization initiator is set to be combined into matching somebody with somebody shown in table 2
In addition, carry out and the same operation of Production Example 20, obtain hydroxyl group containing polyester resin (B-2)~(B-9) that solid content is 50% molten
Liquid.The number-average molecular weight of obtained each hydroxyl group containing polyester resin, hydroxyl value are shown in table 2 in the lump.
[table 3]
[table 4]
[manufacture of coating composition]
Embodiment and comparative example
By as, with composition (A), composition (B) and mineral black is mixed in the way of being combined into, making is solid shown in table 3
Each host that shape thing is about 40%.The solidification of composition (C) is added in the host in the way of being combined into as matching somebody with somebody shown in table 3
Agent is simultaneously equably mixed.Then, retarder thinner is added in obtained mixture, the utilization Ford cup No.4 obtained at 20 DEG C is surveyed
Fixed viscosity is the coating composition of 25 seconds.
In addition, table 3 represents for solid content, (C-1) in table 3~(C-3) is as described below.
(C-1)：デ ュ ラ ネ ー ト 24A-90E, trade name, chemical company of Asahi Chemical Industry manufacture, with the isocyanic acid of hexa-methylene two
Ester is biuret-containing Quito isocyanate compound of raw material, solid content 90%, NCO containing ratio 21.2%
(C-2)XP2580：Trade name, Bayer companies manufacture, using hexamethylene diisocyanate as the first containing urea groups of raw material
Perester radical polyisocyanate compound, solid content 100%, NCO containing ratio 19.5%
(C-3)スミジュールN3300：Trade name, Sumitomo Bayer Urethane companies manufacture, hexa-methylene two is different
The urea acid esters body of cyanate, solid content 100%, NCO containing ratio 21.8%
In addition, mineral black described in table 3 with dispersant (" ソ Le ス パ ー ズ 37500 ", trade name, ル ー Block リ ゾ
ー Le company manufactures) 1 part be pre-mixed after coordinate.
[making of experiment coated plate]
As above made on ABS plates (black, through ungrease treatment) by solidifying thickness air-atomizing application in the way of about 25 μm
Each coating composition made, heating solidifies it in 30 minutes at 80 DEG C, obtains each experiment coated plate.
By obtained each experiment coated plate for following performance tests.Result is shown in table 3 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, damage is caused to film.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 the direction of light incidence vertically (relative to damaging as vertical direction), acceptance angle is the L values in 15 degree of directions (by it
Referred to as L15 ° value), calculate L15 ° of difference Δ before and after 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, in coated surface laminating cellophane adhesive tape and cloth adhesive tape, 20
After it is sharp peeled off at DEG C, the number for the grid that investigation film is remained is 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, the cosmetics on surface are wiped,
Evaluate appearance of film, pencil hardness and tack.
The measure of pencil hardness is carried out by the method same with the above method, is from above-mentioned " lead by pencil hardness mark
Hardness：" item in obtained hardness mark situation about declining within 2 grades be set to qualified.
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
[table 5]
[table 6]
[table 7]
[table 8]
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 day filed in September in 2013 9 days
Present patent application (Japanese Patent Application 2013-186025), its content is incorporated herein by reference.
Claims (5)
1. a kind of coating composition, it is the Coating material composition of the curing agent comprising host and containing polyisocyanate compound (C)
Thing, the host contains hydroxy acryl acid resin (A) and hydroxyl group containing polyester resin (B), wherein,
The hydroxyl value of hydroxy acryl acid resin (A) is 100 to 200mgKOH/g, and glass transition temperature is less than -20 DEG C,
The hydroxy acryl acid resin (A) be on the basis of polymerism unsaturated monomer (a1)~(a3) total amount, make 15 to
The polymerism of 35 mass % methyl methacrylate (a1), 5 to the 30 quality % hydroxy alkyl with carbon number 4~9
Hydroxyl third obtained from unsaturated monomer (a2) and 35 to 80 quality % other polymerism unsaturated monomers (a3) reaction
Olefin(e) acid resin,
The hydroxyl value of hydroxyl group containing polyester resin (B) is that 50 to 200mgKOH/g, number-average molecular weight is 2,000 to 20,000, and institute
State hydroxyl group containing polyester resin (B) be by hydroxyl group containing polyester resin obtained from the reaction of polyalcohol and polyacid, it is described polynary
Alcohol includes the cyclic polyol alcoholic compound (b1) with urea acrylate structure,
Polyisocyanate compound (C) is selected from different by biuret-containing Quito isocyanate compound and special allophanates containing Quito
At least one in the group that cyanate esters are constituted,
The glass transition temperature of resulting film is 20 to 60 DEG C.
2. coating composition according to claim 1, wherein, on the basis of the resin solid quality in host, contain
The mass parts of hydroxy acryl acid resin (A) 10 to 80, the mass parts of hydroxyl group containing polyester resin (B) 20 to 90.
3. coating composition according to claim 1 or 2, wherein, between the crosslinking of obtained film molecular weight be 300 to
1000。
4. a kind of coating process, wherein the application Coating material composition according to any one of claim 1 to 3 on plastic basis material
Thing.
5. a kind of coated article, it is by the application coating according to any one of claim 1 to 3 on plastic basis material
Obtained from composition.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013-186025 | 2013-09-09 | ||
| JP2013186025 | 2013-09-09 | ||
| PCT/JP2014/063893 WO2015033624A1 (en) | 2013-09-09 | 2014-05-26 | Coating composition and coated article |
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| Publication Number | Publication Date |
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| CN105658747A CN105658747A (en) | 2016-06-08 |
| CN105658747B true CN105658747B (en) | 2017-09-29 |
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| CN201480049628.9A Active CN105658747B (en) | 2013-09-09 | 2014-05-26 | Coating composition and coated article |
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| Country | Link |
|---|---|
| JP (1) | JP5692481B1 (en) |
| CN (1) | CN105658747B (en) |
| WO (1) | WO2015033624A1 (en) |
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| JP6917694B2 (en) * | 2016-11-04 | 2021-08-11 | サカタインクス株式会社 | Matte coating agent, matte coating layer, and laminated film |
| 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 |
| CN107177289B (en) * | 2017-06-13 | 2020-05-29 | Ppg涂料(天津)有限公司 | One-component coating composition and substrates coated therewith |
| JP7074984B2 (en) * | 2017-11-29 | 2022-05-25 | 関西ペイント株式会社 | Aqueous 2-component 1-coat paint composition |
| JP2019172811A (en) * | 2018-03-28 | 2019-10-10 | 東洋紡株式会社 | Copolymerized polyester resin and adhesive composition containing 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 |
| WO2020007696A1 (en) * | 2018-07-02 | 2020-01-09 | Akzo Nobel Coatings International B.V. | Two-component solvent-based coating composition, method for coating a substrate, coated substrate, and use of such coating composition for improving erosion resistance |
| JP2020037637A (en) * | 2018-09-03 | 2020-03-12 | 富士ゼロックス株式会社 | Surface protective resin member, laminated resin member, and liquid set |
| JP6955129B2 (en) | 2019-03-28 | 2021-10-27 | 大日精化工業株式会社 | Paint composition and paint film |
| CN109971292A (en) * | 2019-04-11 | 2019-07-05 | 益帆涂料(无锡)有限公司 | A kind of scratch-resistant can laser carving automobile interior decoration coating and its spraying method |
| JP7420513B2 (en) * | 2019-09-17 | 2024-01-23 | 株式会社ダイセル | Composition and cured product thereof |
| JP7461754B2 (en) * | 2020-02-20 | 2024-04-04 | 株式会社ダイセル | Polyisocyanate compound, polyurethane resin-forming composition using the same, and cured product thereof |
| CN112500808B (en) * | 2020-12-02 | 2022-04-15 | 合肥乐凯科技产业有限公司 | Antibacterial paint surface protective film |
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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 |
| DE3322037A1 (en) * | 1983-06-18 | 1984-12-20 | Basf Farben + Fasern Ag, 2000 Hamburg | COATING SIZE, ESPECIALLY FOR THE PRODUCTION OF A TRANSPARENT TOP LAYER |
| EP0653468A3 (en) * | 1993-11-12 | 1995-12-13 | Herberts & Co Gmbh | Coating for clear-coat top layers and its use in processes for preparing multi-layer coatings. |
| 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 |
| US6294607B1 (en) * | 1999-09-08 | 2001-09-25 | Arco Chemical Technology, L.P. | Ultra-high-solids acrylic 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 |
| JP2002275415A (en) * | 2001-03-21 | 2002-09-25 | Kansai Paint Co Ltd | Two-pack type coating composition |
| WO2002088215A2 (en) * | 2001-04-30 | 2002-11-07 | Basf Corporation, Please See General Appointment Of Representative | Sandable, self-healable coating compositions and a process of using the same |
| CA2487916A1 (en) * | 2003-12-04 | 2005-06-04 | Rohm And Haas Company | One-component flexible etch resistant clearcoat |
| JP4872247B2 (en) * | 2005-06-16 | 2012-02-08 | Ｂａｓｆコーティングスジャパン株式会社 | Thermosetting coating composition |
| 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 |
| JP4368395B2 (en) * | 2007-08-22 | 2009-11-18 | Ｂａｓｆコーティングスジャパン株式会社 | Coating composition, coating finishing method, and coated article |
| JP5885192B2 (en) * | 2011-12-29 | 2016-03-15 | 関西ペイント株式会社 | Metallic paint composition |
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| Publication number | Publication date |
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| WO2015033624A1 (en) | 2015-03-12 |
| JPWO2015033624A1 (en) | 2017-03-02 |
| JP5692481B1 (en) | 2015-04-01 |
| CN105658747A (en) | 2016-06-08 |
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