CN110099799A - The protective layer used resin combination of transfer paper, its manufacturing method, laminated body and decoration use transfer paper - Google Patents
The protective layer used resin combination of transfer paper, its manufacturing method, laminated body and decoration use transfer paper Download PDFInfo
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- CN110099799A CN110099799A CN201880005147.6A CN201880005147A CN110099799A CN 110099799 A CN110099799 A CN 110099799A CN 201880005147 A CN201880005147 A CN 201880005147A CN 110099799 A CN110099799 A CN 110099799A
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- protective layer
- transfer paper
- solvent
- resin combination
- layer used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/24—Layered products comprising a layer of synthetic resin characterised by the use of special additives using solvents or swelling agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B44—DECORATIVE ARTS
- B44C—PRODUCING DECORATIVE EFFECTS; MOSAICS; TARSIA WORK; PAPERHANGING
- B44C1/00—Processes, not specifically provided for elsewhere, for producing decorative surface effects
- B44C1/16—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like
- B44C1/165—Processes, not specifically provided for elsewhere, for producing decorative surface effects for applying transfer pictures or the like for decalcomanias; sheet material therefor
- B44C1/175—Transfer using solvent
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/86—Glazes; Cold glazes
-
- 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
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Structural Engineering (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Paints Or Removers (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The protective layer used resin combination of transfer paper of the invention is the protective layer used resin combination of transfer paper containing acrylic acid series polymeric compounds (A), solvent (B), defoaming agent (C) and plasticizer (D), and acrylic acid series polymeric compounds (A) contain the monomeric unit that (methyl) alkyl acrylate that the carbon atom number from alkyl of 50 mass % or more is 3~12 is added up to relative to whole monomeric units；The kinematic viscosity that selected from 25 DEG C at according to the method for ASTM D445 measures of the solvent (B) containing 70 mass % or more is in 1.5mm2At least one kind of solvent (B1) in/s cycloalkanes series solvent below and isoparaffin series solvent, aromatic compound is below 2 mass %.
Description
Technical field
The present invention relates to the protective layer used resin combination of transfer paper, its manufacturing method, laminated body and decoration transfer papers.
The Patent 2017-007245 CLAIM OF PRIORITY that the application submits application in Japan based on January 19th, 2017, is helped herein
Draw its content.
Background technique
All the time, (following to be also known as in plastics, timber, metal, ceramics, glass, enamel, ceramic tile, other ceramics etc.
" ware etc. ") on decoration, be widely used that using be successively laminated with base stock, W Sol P layer, printing be desired figure
The printing ink layer of case, the decoration of protective layer single paper transfer printing of transfer paper.In this method, firstly, transfer paper is immersed in
In water or warm water, the lower protective layer with printing ink layer is removed from base stock, transfer paper is pasted onto the regulation of ware etc.
On position, make printing ink layer in inside.Then, the moisture and bubble etc. between protective layer such as ware are removed, keeps it dry
It is dry.Finally, removing protective layer by firing or removing, printing ink layer is transferred to the surface of ware etc., it is possible thereby into
Luggage decorations.
As for manufacturing resin contained in the protective layer used resin combination of decoration transfer paper, such as third can be enumerated
The resin of olefin(e) acid system resin, vinyl acetate resin, alkyd resin, polyester resin and cellulose-based resin etc..Wherein, especially
It is suitble to use acrylic resin.Acrylic resin can be copolymerized in any combination since the type of starting monomer is abundant,
Therefore it be free to obtain the resin of the glass transition temperature with wide scope and molecular weight.Therefore, containing acrylic acid
It is the protective layer used resin combination of resin, good with printing adaptability, the protective layer of formation Physical properties of coating film is easily adjusted
Such desired characteristics.
It is recorded in patent document 1 and is mixed with solvent SWASOL (registered trademark) 1000, i.e. industrial naptha is protective layer used
Resin combination.Bubble and pit are less due to being formed by protective layer for the resin combination, and printing characteristic is also excellent,
But due to containing aromatic compound in solvent, there is a problem of that foul smell is strong.
Existing technical literature
Patent document
Patent document 1: Japanese Patent Laid-Open 2003-183559 bulletin
Summary of the invention
Subject to be solved by the invention
The object of the present invention is to provide a kind of protective layer used resin combination of transfer paper and its manufacturing method, laminated body and
Decoration transfer paper, the protective layer used resin combination of the transfer paper are that covering print is used to form in manufacture of the decoration with transfer paper
The resin combination of the protective layer of brush ink layer, bubble and pit are few on protective layer, and foul smell is few.
To the means to solve the problem
A kind of protective layer used resin combination of transfer paper of 1 > of <, be containing acrylic acid series polymeric compounds (A), solvent (B) and
The protective layer used resin combination of transfer paper of plasticizer (D), acrylic acid series polymeric compounds (A) are originated from alkane containing 50 mass %'s or more
The monomeric unit of (methyl) alkyl acrylate that the carbon atom number of base is 3~12；Solvent (B) is molten containing 70 mass %'s or more
Agent (B1), the solvent (B1) are according to the kinematic viscosity of the method measurement of ASTM D445 at 25 DEG C in 1.5mm2/ s with
Under cycloalkanes series solvent and isoparaffin series solvent in it is at least one kind of, aromatic compound is below 2 mass %.
2 > of < protective layer used resin combination of transfer paper according to above-mentioned 1 > of <, acrylic acid series polymeric compounds (A) contain 50
The monomeric unit and 10~50 matter for the alkyl methacrylate that the carbon atom number from alkyl of~90 mass % is 3~6
The monomeric unit for the alkyl methacrylate that the carbon atom number from alkyl for measuring % is 7~12.
3 > of < protective layer used resin combination of transfer paper according to above-mentioned 1 > of < or 2 > of <, the composition also contain
Defoaming agent (C).
4 > of < protective layer used resin combination of transfer paper according to above-mentioned 3 > of <, the acrylic acid relative to 100 mass parts
Based polymer (A), the composition contain the solvent (B) of 70~500 mass parts, the defoaming agent (C) of 0.1~15 mass parts, 5~
The plasticizer (D) of 35 mass parts.
5 > of < protective layer used resin combination of transfer paper according to above-mentioned 3 > of < or 4 > of <, defoaming agent (C) are poly- silicon oxygen
Alkane or acrylic compounds.
6 > of < protective layer used resin combination of transfer paper according to any one in above-mentioned 1 > of <~<, 5 >, it is described
The weight average molecular weight of acrylic acid series polymeric compounds (A) is 50,000~200,000.
7 > of the < protective layer used resin combination of transfer paper, institute according to any one in above-mentioned 1 > of <~<, 6 >
The glass transition temperature of acrylic acid series polymeric compounds (A) is stated at 10 DEG C or more.
8 > of < transfer paper resin combination according to any one in above-mentioned 1 > of <~<, 7 >, plasticizer (D) are
Polyester, benzoic acid system or phthalic acid ester system plasticizer.
A kind of manufacturing method of the protective layer used resin combination of transfer paper of 9 > of < is appointing in above-mentioned 1 > of <~<, 8 > of manufacture
The method of the protective layer used resin combination of transfer paper described in meaning one, mixing acrylic acid series polymeric compounds (A), at 25 DEG C according to
According to ASTM D445 method measurement kinematic viscosity in 1.5mm2/ s cycloalkanes series solvent below and isoparaffin series solvent
At least one kind of solvent (B1) and plasticizer (D).
The manufacturing method of 10 > of < protective layer used resin combination of transfer paper according to above-mentioned 9 > of <, goes back mixture foam killer
(C)。
A kind of laminated body of 11 > of <, be sequentially laminated with base stock, W Sol P layer, printing ink layer, by above-mentioned 1 > of <~< 8
The protective layer that the dried object of the protective layer used resin combination of transfer paper described in any one in > is constituted.
A kind of decoration transfer paper of 12 > of <, the laminated body described in above-mentioned 11 > of < are constituted.
Invention effect
According to the present invention it is possible to provide bubble and the protective layer used resin group of the transfer paper that pit is few, foul smell is few on protective layer
Close the laminated body of object and its manufacturing method, and the decoration transfer paper with the less protective layer of bubble and pit etc..
Detailed description of the invention
[Fig. 1] is the summary sectional view for showing an embodiment of decoration transfer paper of the invention.
The explanation of symbol
1 decoration uses transfer paper
3 base stocks
5 W Sol P layers
7 printing ink layers
9 protective layers
Specific embodiment
In this specification and claims, so-called " (methyl) acrylate " is acrylate and methacrylate
General name.So-called " (methyl) acrylic acid " is the general name of acrylic acid and methacrylic acid.
(the protective layer used resin combination of transfer paper)
The protective layer used resin combination of transfer paper of the invention (following to be only called " resin combination " again) is poly- containing acrylic acid series
Close object (A), solvent (B) and plasticizer (D).Solvent (B1) of the solvent (B) containing 70 mass % or more, the solvent (B1) are choosing
The kinematic viscosity measured from 25 DEG C according to the method for ASTM D445 is in 1.5mm2/ s cycloalkanes series solvent below and isomeric alkane
It is at least one kind of in hydrocarbon system solvent.Solvent (B) can also contain the solvent (B2) other than solvent (B1).In addition, solvent (B) is contained
Aromatic compound below 2 mass %.
Defoaming agent (C) can also be contained in resin combination.
Other additives can also be contained in resin combination.
< acrylic acid series polymeric compounds (A) >
Acrylic acid series polymeric compounds (A) contain the monomer of (methyl) alkyl acrylate that the carbon atom number from alkyl is 3~12
Unit.
The specific example of (methyl) alkyl acrylate that the carbon atom number as alkyl is 3~12, such as (methyl) can be enumerated
Propyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) third
The secondary butyl ester of olefin(e) acid, (methyl) cyclohexyl acrylate, (methyl) 2-EHA and (methyl) lauryl base
Ester etc..These can be used alone any one or a variety of uses of combination.In addition, based on molten in aftermentioned solvent (B)
The viewpoint of solution property, the substance that the carbon atom number of the more preferable alkyl of (methyl) alkyl acrylate is 4~8.
In acrylic acid series polymeric compounds (A), the list of (methyl) alkyl acrylate that the carbon atom number from alkyl is 3~12
The content of body unit is 50 mass % or more, preferably 90 mass % or more relative to the total of whole monomeric units, more preferably
95 mass % or more.If the content of the monomeric unit from (methyl) alkyl acrylate more than the lower limit value,
The excellent strength of protective layer.The upper limit of the content of the monomeric unit from (methyl) alkyl acrylate has no special limit
It is fixed, it is also possible to 100 mass %.
Acrylic acid series polymeric compounds (A) preferably comprise the list of the alkyl methacrylate of the carbon atom number 3~6 from alkyl
The monomeric unit of body unit and the alkyl methacrylate of the carbon atom number 7~12 from alkyl.Carbon atom from alkyl
The monomeric unit of the alkyl methacrylate of number 3~6 can promote dissolubility of the polymer (A) in solvent (B1), make to protect
Sheath becomes soft.The monomeric unit of the alkyl methacrylate of carbon atom number 7~12 from alkyl, can further mention
Rise the dissolubility of polymer (A) in solvent (B1).Acrylic acid series polymeric compounds (A) preferably comprise 50~90 mass % be originated from alkane
The carbon from alkyl of the monomeric unit of the alkyl methacrylate of the carbon atom number 3~6 of base and 10~50 mass % are former
The monomeric unit of the alkyl methacrylate of subnumber 7~12.
In acrylic acid series polymeric compounds (A), (methyl) acrylic acid that can also be 3~12 containing the carbon atom number from alkyl
The monomeric unit of other monomers other than Arrcostab.
As other monomers, as long as (methyl) alkyl acrylate copolymer that can be 3~12 with the carbon atom number of alkyl
Substance, such as the vinyl monomer of simple function can be enumerated.As the specific example of such vinyl monomer, such as can lift
(methyl) alkyl acrylate of the carbon atom number of (methyl) methyl acrylate, (methyl) ethyl acrylate and alkyl 13 or more out
The α of (methyl) alkyl acrylate, (methyl) acrylic acid, maleic acid, itaconic acid and the crotonic acid of base ester etc. etc., the mono- ethylene of β-
Property unsaturated carboxylic acid, (methyl) 2-hydroxyethyl acrylate, (methyl) acrylic acid -2- hydroxypropyl ester and (methyl) acrylic acid -
(methyl) hydroxyalkyl acrylates, (methyl) acrylic acid diethylamino ethyl ester and (methyl) propylene of 4- hydroxyl butyl ester etc.
The fragrance of amino-containing (methyl) alkyl acrylate, styrene and the α-methylstyrene of sour dimethylamino ethyl ester etc. etc.
Race's mono-vinyl monomer, vinylacetate, vinyl propionate and (methyl) acrylonitrile etc..These can be used alone any 1
Kind, or multiple combinations are used alone and use.
As other monomers, based on the viewpoint for the tensile strength for embodying protective layer, preferably α, the mono- ethylene unsaturation carboxylic of β-
Sour and amino-containing (methyl) alkyl acrylate, more preferable (methyl) acrylic acid and (methyl) acrylic acid diethylamino
Ethyl ester.
Based on obtaining the viewpoint of good Adhesion Resistance, the glass transition temperature adhesiveness of acrylic acid series polymeric compounds (A)
Preferably 10 DEG C or more, more preferable 20~70 DEG C.Glass transition temperature is higher, is formed by protective layer and is more difficult to adhere to
Property, Adhesion Resistance more becomes good.
The glass transition temperature of acrylic acid series polymeric compounds (A) can pass through according to the type and mass fraction of monomeric unit
Fox equation represented by following (1) formulas acquires.
1/Tg=Σ (Wi/Tgi)·····(1)
In above-mentioned (1) formula, Tg indicates the glass transition temperature (unit K) of acrylic acid series polymeric compounds (A), WiIt indicates to be originated from structure
At the mass fraction of the monomeric unit of the monomer i of acrylic acid series polymeric compounds (A), TgiIndicate that the vitrifying of the self-aggregate of monomer i turns
Temperature (unit K).POLYMERHANDBOOK Volume 1 (WILEY-INTERSCIENCE) note can be used in the value of Tgi
The value of load.
The viewpoint of film forming based on resin combination, the tensile properties of protective layer when being removed from printing ink layer etc.,
The weight average molecular weight of acrylic acid series polymeric compounds (A) is preferably 50,000~200,000, more preferable 70,000~150,000.Propylene
The weight average molecular weight of sour based polymer (A) is bigger, and the tensile properties of the protective layer obtained from resin combination are more excellent.In addition,
The weight average molecular weight of acrylic acid series polymeric compounds (A) is smaller, and the viscosity of resin combination is more sufficiently lower, and is protected by formation such as printings
Film forming when sheath more becomes excellent.In addition, the weight average molecular weight of the acrylic acid series polymeric compounds (A) illustrated in the present invention is basis
GPC-LS method (Gel Permeation Chromatography-Light Scattering Method:GPC- light scattering method)
The value of the polystyrene conversion of measurement.
Acrylic acid series polymeric compounds (A) can be by well known to suspension polymerisation, polymerisation in solution, bulk polymerization or emulsion polymerization etc.
Polymerization manufacture.In these methods, based on acrylic acid series polymeric compounds (A) molecular weight, the resin for being easy to make
The sight for the advantages that freedom degree of the solvent selection of composition increases, resin combination high solid can be made to break up or is solvent-free
Point preferably can be used as the suspension polymerisation that solid type particle obtains acrylic acid series polymeric compounds (A).
< solvent (B) >
Solvent (B) exists at 25 DEG C according to the kinematic viscosity that the method for ASTM D445 measures containing 70 mass %'s or more
1.5mm2At least one kind of solvent (B1) in/s cycloalkanes series solvent below and isoparaffin series solvent.It is viscous compared to movement
Degree is more than 1.5mm2The cycloalkanes series solvent and/or isoparaffin series solvent of/s, solvent (B1) can make resin combination at
Film property becomes good.
As solvent (B1), for example, can enumerate ethane, heptane, Exxon Mobil Corporation manufacture EXXSOL (registered trademark)
Cycloalkanes series solvent, the Exxon Mobil of DSP80/100, EXXSOL DSP100/120, EXXSOL D30 and EXXSOL D40 etc.
The few solvent of the aromatic content of the paraffin series solvent of ISOPAR (registered trademark) E the and ISOPAR G of company's manufacture etc. etc..
Wherein, as solvent (B1), the viewpoint of the film forming based on resin combination, preferably EXXSOL D30, EXXSOL D40 and
ISOPAR G.Solvent (B1) can be used alone above-mentioned solvent, or also two or more kinds may be used.Solvent (B1) can also be with
Be be mixed together with acrylic acid series polymeric compounds (A), defoaming agent (C) and the other compositions such as plasticizer (D) and additive it is molten
Agent.
Solvent (B) can also contain the solvent (B2) other than solvent (B1).As the solvent (B2) other than solvent (B1), base
In the viewpoint for promoting resin compatible and printing etc., can be mixed the substance among being exemplified below as solvent (B).
That is, as solvent (B2), such as the aromatic system solvent that toluene, dimethylbenzene and ethylbenzene can be enumerated etc.；Ethyl acetate, acetic acid are just
The acetic acid ester series solvent of butyl ester, isobutyl acetate, n-propyl acetate, isopropyl acetate and pentyl acetate etc.；Methyl-isobutyl
The ketone series solvent of ketone, methyl ethyl ketone, diisobutyl ketone and acetone etc.；Methanol, ethyl alcohol, isopropanol, normal propyl alcohol, n-butanol,
The alcohol of isobutanol, the tert-butyl alcohol, benzylalcohol, diacetone alcohol, dipropylene glycol n-propyl ether, dipropylene glycol methyl ether and Propylene glycol n-propyl ether etc.
Series solvent；Two alcohol series solvents of ethylene glycol, diethylene glycol, triethylene glycol and propylene glycol etc.；Ethylene glycol monoethyl ether, ethylene glycol list
The glycol ether series solvent of butyl ether etc.；The acetic acid ester series solvent of methyl glycol acetate and acetic acid methoxyl group propyl ester etc.；Just oneself
The hydrocarbon system solvent of alkane, cyclohexane, methyl cyclohexane and heptane etc.；The EXXSOL (registered trademark) of Exxon Mobil Corporation's manufacture
The cycloalkanes series solvent of D80, EXXSOL D110 and EXXSOL D130 etc.；ISOPAR (the registration of Exxon Mobil Corporation's manufacture
Trade mark) H, ISOPAR L and ISOPAR M etc. paraffin series solvent；The SOLVESSO (registered trademark) of Exxon Mobil Corporation
100, SWASOL (registered trademark) 1000, SWASOL that SOLVESSO 150, SOLVESSO 200, Maruzen Oil Company manufacture
1500, the stone brain of SWASOL 1800, the IPZOLE (registered trademark) 100 that Chu Guangxingchan company manufactures and IPZOLE 150 etc.
Oily series solvent etc..These solvents can be used alone, and also may be two kinds or more and uses.Solvent (B2) is also possible to third
The solvent that olefin(e) acid based polymer (A), defoaming agent (C) and the other compositions such as plasticizer (D) and additive mix jointly.
In resin combination of the invention, relative to 100 mass parts of acrylic acid series polymeric compounds (A), the combined amount of solvent (B)
It is preferred that 70~500 mass parts, more preferable 100~400 mass parts, based on the viewpoint for the bubble for reducing protective layer, further preferably
150~300 mass parts.The combined amount of solvent (B) is more, and the bubble of protective layer more tails off.In addition, the combined amount of solvent (B) is got over
Few, the thickness of protective layer more thickens, easier to remove from base stock.
Content shared by solvent (B1) in solvent (B) is 70 mass % or more as described above.Namely based on the gas for reducing protective layer
The viewpoint of bubble, content is more than 70 mass %, preferably 80 mass % or more.
In addition, the content of solvent (B2) is the remnants of solvent (B1), in 30 mass % hereinafter, it is preferred that 20 mass % or less.When molten
When agent (B2) contains aromatic series, the fewer the content of the viewpoint based on foul smell, solvent (B2) the better.
In addition, solvent (B1) and solvent (B2) are selected, so that fragrance contained by solvent (B) in resin combination of the invention
Race's content is below 2 mass %.Viewpoint based on foul smell, the fewer aromatic content the better, preferably 1.5 mass % or less.Fragrance
Race's content is generally measured by gas chromatography.
< defoaming agent (C) >
Defoaming agent (C) is the additive for preventing bubble or making the bubbles burst generated.As defoaming agent (C), such as can lift
Poly- alkyl dimethicone, polyether-modified dimethyl silicone polymer, polyester modification dimethyl silicone polymer, polyether-modified poly- out
Methyl alkyl siloxane, aralkyl modified poly- methyl alkyl siloxane, polyether modified siloxane and contain polyester modification hydroxyl
Dimethyl silicone polymer etc. using polysiloxanes as the silicone-based defoaming agent of active constituent, with the poly- of acrylic compounds etc.
It closes the non-silicone polymer system defoaming agent that object is active constituent and the mineral oil system for making hydrophobic particles be scattered in carrier oil disappears
Infusion etc..As defoaming agent (C), the viewpoint based on film forming, preferably silicone-based defoaming agent and non-silicone polymer system disappear
Infusion is more preferably using poly- alkyl dimethicone as the silicone-based defoaming agent of active constituent and with acrylic compounds
The non-silicone polymer system defoaming agent of active constituent.
In resin combination of the invention, relative to 100 mass parts of acrylic acid series polymeric compounds (A), when mixture foam killer (C)
Combined amount preferably 0.1~15 mass parts, the viewpoint of the balance based on the bubble and protective layer intensity that are further reduced protective layer,
More preferable 0.3~5.0 mass parts.The combined amount of defoaming agent (C) is more, and the bubble of protective layer more tails off, therefore protective layer is strong
Degree more increases.
< plasticizer (D) >
Plasticizer (D) is that have the additive of acrylic acid series polymeric compounds (A) ability being plasticized.As plasticizer (D), such as can
Enumerate phthalic acid ester, phosphate, adipate ester and ether based compound.As phthalic acid ester, such as neighbour can be enumerated
Dibatyl phithalate, dihexyl phthalate, dioctyl phthalate, diisononyl phthalate and adjacent benzene two
The bialkyl ortho phthalate of formic acid diisodecyl ester etc.；The phthalic acid alkyl benzyl of butyl benzyl phthalate etc.
Ester；Alkyl aryl phthalate；Dibenzyl phthalate；Diaryl phthalates etc..As phosphate, can lift
The phosphate of the tri aromatic ester of phosphic acid system, trialkylphosphate system and alkyl aryl phosphate system etc. of tricresyl phosphate etc. out.
As adipate ester, the fatty group dibasic acid of dibutyl adipate and dioctyl adipate etc. can be enumerated.As ether system
Close object, such as polyethylene glycol, polypropylene glycol and the sweet ester of adipic acid dibutyl two can be enumerated etc..As plasticizer (D), except this with
The plasticising of soybean oil system of benzoic acid system, trimellitic acid system and Polyester and epoxidised soybean oil etc. etc. can also be used outside
Agent.These plasticizer not only can be used alone, but also plasticizer of more than two kinds can be used in mixed way.In addition, making
For plasticizer (D), the viewpoint of the film forming based on resin combination, preferably phthalic acid ester, adipate ester, benzoic ether with
And trimellitate, more preferable dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, adjacent benzene two
Formic acid dinonyl, diisooctyl phthalate, dibutyl adipate, dioctyl adipate, trioctyl trimellitate (TOTM), inclined benzene
Three acid, three (2- ethylhexyl) ester and benzoic ether, particularly preferred dioctyl phthalate, diisononyl phthalate,
Dioctyl adipate, trioctyl trimellitate (TOTM) and benzoic ether.
In resin combination of the invention, relative to 100 mass parts of acrylic acid series polymeric compounds, the combined amount of plasticizer (D)
Preferably 5~35 mass parts, the viewpoint of the intensity of operability and protective layer when based on balance transfer pattern, more preferable 7~20
Mass parts.The combined amount of plasticizer (D) is more, and protective layer more limbers up, therefore the operation in the upper transfer pattern such as ware
Property promoted.On the other hand, the combined amount of plasticizer (D) is fewer, and the intensity of protective layer is more got higher.
< others ingredient >
In resin combination of the invention, in addition to (A), (B), (C) and (D) ingredient, additive etc. can also be added
Other compositions.As such additive, such as viscosity stability, the softness when being coated with for being promoted with the methods of printing can be enumerated
The auxiliary agents such as the thixotropic agent of property, drying property etc..As thixotropic agent, such as amide system wax, the castor that fatty acid acyl amine system wax can be enumerated etc.
Sesame oil and rilanit special etc..
In resin combination of the invention, relative to 100 mass parts of acrylic acid series polymeric compounds (A), the mixing of other compositions
Below the mass, more preferable 10 below the mass for amount preferably 15.The combined amount of other compositions is fewer, and resin combination is passed through silk
Coating adaptability when wire mark brush etc. is coated with and forms protective layer has the tendency that promotion.
< resin combination >
The solid concentration of resin combination of the invention is preferably 20~50 mass %, more preferable 25~45 mass %.This is solid
Shape object concentration is lower, and the viscosity of resin combination is more lower.On the other hand, the solid concentration of resin combination is higher, film
More thicken, it is easier to be attached on ware etc..Herein, the solid content illustrated in this specification refers to the institute other than solvent
There is ingredient.
The viscosity of resin combination of the invention is preferably 100~5000mPas, more preferable 500~3000mPas.
The viscosity of the resin combination illustrated in this specification is the value measured using Brookfield viscometer with 25 DEG C, revolving speed 60rpm.Resin
The viscosity of composition is lower, and coating adaptability when resin combination is formed protective layer by the coating such as silk-screen printing more mentions
It rises.On the other hand, the viscosity of resin combination is higher, and film more thickens, and becomes easier and protective layer is attached on ware etc..
The viscosity of resin combination can mainly be adjusted by the combined amount of solvent (B).
The manufacturing method > of < resin combination
Resin combination of the invention, can be by mixing acrylic acid series polymeric compounds (A), being selected from 25 DEG C according to ASTM D445
The kinematic viscosity of method measurement is in 1.5mm2At least one kind of solvent in/s cycloalkanes series solvent below and isoparaffin series solvent
(B1) and plasticizer (D) and manufacture.At this point, as needed, it can be with the other compositions of mixture foam killer (C) and additive etc..
As the manufacturing method of resin combination of the invention, preferably following method: by solvent (B1) loading have blender,
The mixing arrangement of cooling tube and thermometer, by it, acrylic acid series polymeric compounds (A) is added in the amount of pursuing while stirring, and confirms propylene
After sour based polymer (A) dissolution, addition defoaming agent (C), plasticizer (D), other additives as needed.Acrylic polymeric
Object (A), defoaming agent (C), plasticizer (D) or other compositions can also mix together with solvent.
The purposes > of < resin combination
Resin combination of the invention may be used as the material of protective layer set on the laminated bodies such as decoration transfer paper.As dress
Decorations transfer paper, such as substance made of having stacked gradually base stock, W Sol P layer, printing ink layer, protective layer can be enumerated.
< function and effect >
Resin combination of the invention contains acrylic acid series polymeric compounds (A), solvent (B) and plasticizer (D), therefore foul smell is low, shape
Film forming when at protective layer is also good, wherein solvent (B) is containing 70 mass % or more according to ASTM at 25 DEG C
The kinematic viscosity of the method measurement of D445 is in 1.5mm2At least 1 in/s cycloalkanes series solvent below and isoparaffin series solvent
Kind solvent (B1), and aromatic compound is below 2 mass %.It is applied for example, resin combination is formed by coatings such as printings
When film, it is difficult to generate bubble and pit on film.Therefore, it is dried and the protective layer that is formed also becomes bubble and pit is less
Substance.
(decoration transfer paper: laminated body)
About laminated body of the invention, by taking decoration transfer paper as an example, referring to attached drawing, embodiments thereof is shown and are illustrated.
Fig. 1 is the summary sectional view for showing an embodiment of decoration transfer paper of the invention.
The decoration of present embodiment be sequentially laminated in transfer paper 1 base stock 3, W Sol P layer 5, printing ink layer 7 and protect
Sheath 9.
W Sol P layer 5 is formed as covering the entire single side of base stock 3.The part shape on W Sol P layer 5 of printing ink layer 7
At.Protective layer 9 is formed as covering printing ink layer 7.A part of protective layer 9 connects with W Sol P layer 5.
As base stock 3, base stock (and paper) of good water absorption etc. can be enumerated.As the water solubility for forming W Sol P layer 5
Paste, such as starch, polyvinyl alcohol and carboxymethyl cellulose can be enumerated etc..
As printing ink layer 7, such as heat fixed type ink, thermoplastic inks and UV curable ink can be enumerated etc..Off-set oil
Layer of ink 7 is formed by the pattern for being transferred to ware etc..Printing ink layer 7 can be single layer, be also possible to multilayer.
Protective layer 9 is made of the dried object of resin combination of the invention above-mentioned, containing acrylic acid series polymeric compounds (A) and
Plasticizer (D).Protective layer 9 can also contain defoaming agent (C) and other additives.
Decoration can be manufactured as follows with transfer paper 1: being for example coated with W Sol P in whole face and formed W Sol P
On the base stock 3 of layer 5, printing ink layer 7 is formed using ink, resin combination of the invention is coated on it, by the resin group
It closes object drying and forms protective layer 9.
As ink, such as heat fixed type ink, thermoplastic inks and UV curable ink can be enumerated etc..
Printing ink layer 7 can be formed by well known method.Such as silk-screen printing, intaglio printing, flexible printing can be passed through
And offset printing etc., ink is coated on W Sol P layer 5, it is enabled to be solidified to form printing ink layer 7 as needed.
As the coating method of resin combination, such as silk-screen printing, intaglio printing, flexible printing and offset printing can be enumerated
Deng.As long as drying for resin combination enables solvent (B) to volatilize.
When using decoration transfer paper 1, such as it can be decorated as follows.
Firstly, decoration transfer paper 1 is immersed in water or warm water, W Sol P layer 5 is dissolved, will have printing ink layer
7 protective layer 9 is removed from base stock 3.The protective layer 9 with printing ink layer 7 is pasted and is transferred such as ware
The specified position of object, so that ware etc. is contiguously pasted with printing ink layer 7.Then, the guarantor for having printing ink layer 7 is removed
Then protective layer 9 is burnt by moisture and bubble between sheath 9 and ware etc. etc., leave printing on the surface of ware etc.
Ink layer 7, thus in the enterprising luggage decorations such as ware.
Embodiment illustrated above illustrates decoration transfer paper of the invention, but the present invention is not limited to above-mentioned embodiment party
Formula.Each composition in above embodiment and combinations thereof etc. is an example, without departing from the spirit and scope of the invention,
Can be constituted it is additional, omit, displacement and other changes.
, can for example, as long as W Sol P layer 5 is set to the position at least formed with printing ink layer 7 and protective layer 9
Not cover the entire single side of base stock 3.
Embodiment
The present invention is described in more detail by the following examples, but these embodiments are not delimit the scope of the invention.In addition,
" part " expression " mass parts " in following embodiment, " % " expression " quality % ".Evaluation method in embodiment is according to below
Method.
(evaluation method)
< film forming >
Using commercially available cylinder press, even spread has base stock (the MURAKAMI company of W Sol P on entire single side
215 × 290mm of SPA processed) on, with the 300 mesh silk-screen printing heat fixed type inks (empire ink corporation MEG) of nylon, formed
The printing ink layer of decorative pattern as decoration is placed 12 hours at room temperature.Then, above again with 60 mesh silk screens of nylon
Printing resin composition forms the film of resin combination, places 1 minute.After placement, the film is visually observed, is implemented as follows
Evaluation, as a result as shown in table 2 below.
It is good: bubble-free or pit.
It is bad: to have bubble or pit.
< foul smell >
Confirm the foul smell of resin combination obtained above, implements its evaluation as follows, as a result as shown in table 2 below.
It is good: not feel pungent odor.
It is bad: to feel pungent odor.
The manufacturing method > of < dispersing agent
In the polyplant for having blender, cooling tube and thermometer, 900 parts of deionized water, methacrylic acid-is added
12 parts of 60 parts of 2-ethanesulfonic acid ester sodium salt, 10 parts of methacrylic acid potassium and methyl methacrylate simultaneously stir, and on one side fill polymerization
Interior progress nitrogen displacement is set, is warming up to 50 DEG C on one side.2,2 '-azo, two (the 2- methyl-prop as polymerization initiator is added thereto
Amidine) 0.08 part of dihydrochloride, then it is warming up to 60 DEG C.After heating, pumped using being added dropwise, by methyl methacrylate with 0.24 part/point
The speed of clock is continuously added dropwise 75 minutes.Terminate after being added dropwise, reaction solution is kept for 6 hours in 60 DEG C, then cools to room temperature, obtains
To the dispersing agent of the solid content 10% of transparent aqueous solution.
The manufacture > of < acrylic acid series polymeric compounds A1
In the polyplant for having blender, cooling tube and thermometer, 145 parts of deionized water, 0.3 part of sodium sulphate is added
And 0.3 part of dispersing agent (solid content 10%) and stir, it is made as uniform aqueous solution.
Then, 81 parts of Isobutyl methacrylate, 19 parts of methacrylic acid -2- ethylhexyl, lauryl mercaptan 0.2 is added
Part, 2,2 ' -0.3 part of azos two (2- methylbutyronitrile), are made as aqueous suspension.
Then, nitrogen displacement will be carried out in polyplant, be warming up to 80 DEG C and react 1 hour, in order to further increase aggregate rate, as
Post-processing temperature is warming up to 90 DEG C, is kept for 60 minutes.Then reaction solution is cooled to 40 DEG C, obtained containing the aqueous of polymer
Suspension.
By 45 μm of mesh of nylon filter-cloth filtering of the aqueous suspension, it is dehydrated after filtrate is washed with deionized water, 40
It is 16 hours dry at DEG C, obtain the acrylic acid series polymeric compounds A1 that 90 parts of weight average molecular weight are 110,000.
In acrylic acid series polymeric compounds A1, according to the inventory of its raw material, the carbon atom number from alkyl containing 100 mass % is
3~12 (methyl) alkyl acrylate monomer units, wherein 81 mass % of Isobutyl methacrylate unit, metering system
19 mass % of acid -2- ethylhexyl unit.In addition, the glass transition temperature of acrylic acid series polymeric compounds A1 is 50 DEG C.
(Examples 1 to 10, the Comparative Examples 1 to 5)
Each raw material is mixed according to combined amount shown in the following table 1 (part), is mixed with high speed disperser, obtains the protective layer used resin of transfer paper
Composition.For obtained resin combination, the evaluation of foul smell and film forming above-mentioned is carried out, result is as shown in table 2 below.
[table 1]
[table 2]
Each ingredient in table 1 is as follows.
A-S-A (registered trademark) T-380-20BS: trade name, her rattan liquefaction corporation fatty acid acyl amine system wax (effective component
20%；Solvent: petroleum series solvent 65%, benzylalcohol 15%)
BYK (registered trademark) -077: trade name, BYK Japan corporation silicone-based defoaming agent (effective component 52%；Solvent: high
Boiling point aromatic solvent)
BYK (registered trademark) -052: trade name, BYK Japan corporation acrylic acid series defoaming agent (effective component 20%；Solvent:
Mineral spirit)
EXXSOL (registered trademark) D30: trade name, Exxon Mobil Corporation's cycloalkanes series solvent (effective component 100%；Movement
Viscosity: 0.99mm2/s；Aromatic content: 0.01% or less)
EXXSOL (registered trademark) D40: trade name, Exxon Mobil Corporation's cycloalkanes series solvent (effective component 100%；Movement
Viscosity: 1.3mm2/s；Aromatic content: 0.05%)
ISOPAR (registered trademark) G: trade name, Exxon Mobil Corporation's isoparaffin series solvent (effective component 100%；Fortune
Kinetic viscosity: 1.49mm2/s；Aromatic content: 0.005% or less)
ISOPAR (registered trademark) L: trade name, Exxon Mobil Corporation's isoparaffin series solvent (effective component 100%；Fortune
Kinetic viscosity: 1.6mm2/s；Aromatic content: 0.01% or less)
ISOPAR (registered trademark) M: trade name, Exxon Mobil Corporation's isoparaffin series solvent (effective component 100%；Fortune
Kinetic viscosity: 3.57mm2/s；Aromatic content: 0.01%)
SWASOL (registered trademark) 1000: trade name, Maruzen Oil Company's fragrance hydrocarbon system solvent (effective component 100%；Movement
Viscosity: 0.9mm2/s；Aromatic content: 100%)
The evaluation result of the resin combination of Examples 1 to 10, foul smell and film forming is good.On the other hand, it uses
The kinematic viscosity for substituting solvent (B1) is more than 1.5mm2In the comparative example 1~2 of the isoparaffin series solvent of/s, when printing, is produced
Bubble or pit etc., film forming is bad.The comparative example 3 of the fragrant hydrocarbon system solvent of substitution solvent (B1) is used and by part
Solvent (B1) is replaced into the comparative example 5 of fragrant hydrocarbon system solvent, since the aromatic content of solvent (B) has been more than 2 mass %, because
This foul smell is strong, it is difficult to operate.The amount of solvent (B1) is set as less than in 70 mass %, the comparative example 4 for 60 mass %, and when printing produces
Bubble or pit etc. are given birth to, film forming is bad.
Industrial availability
The protective layer used resin combination of transfer paper according to the present invention, can be in the transfer paper decorated to transferred object
Deng laminated body in, form bubble or pit is few and foul smell is few protective layer, therefore be particularly suitable for being used as example in ware
The protective layer formation resin combination for the transfer paper that equal surfaces are decorated.
Claims (12)
1. a kind of protective layer used resin combination of transfer paper, to contain acrylic acid series polymeric compounds A, solvent B and plasticizer D
The protective layer used resin combination of transfer paper, acrylic acid series polymeric compounds A contain the carbon atom number from alkyl of 50 mass % or more
For the monomeric unit of 3~12 (methyl) alkyl acrylate；Solvent B contain 70 mass % or more at 25 DEG C according to
The kinematic viscosity of the method measurement of ASTM D445 is in 1.5mm2In/s cycloalkanes series solvent below and isoparaffin series solvent
At least one kind of solvent B1, aromatic compound is below 2 mass %.
2. the protective layer used resin combination of transfer paper according to claim 1, acrylic acid series polymeric compounds A contain 50~90 matter
Measure the carbon atom number from alkyl of % for 3~6 alkyl methacrylate monomeric unit and 10~50 mass %
The monomeric unit for the alkyl methacrylate that carbon atom number from alkyl is 7~12.
3. the protective layer used resin combination of transfer paper according to claim 1 or 2, the composition also contain defoaming agent C.
4. the protective layer used resin combination of transfer paper according to claim 3, the acrylic acid series relative to 100 mass parts is poly-
Close object A, the plasticizer D of the defoaming agent C of solvent B, 0.1~15 mass parts containing 70~500 mass parts, 5~35 mass parts.
5. the protective layer used resin combination of transfer paper according to claim 3 or 4, defoaming agent C is polysiloxanes or propylene
Sour based compound.
6. the protective layer used resin combination of transfer paper according to any one of claims 1 to 5, the acrylic acid series
The weight average molecular weight of polymer A is 50,000~200,000.
7. the protective layer used resin combination of transfer paper according to any one of claims 1 to 6, the acrylic acid
The glass transition temperature of based polymer A is at 10 DEG C or more.
8. transfer paper resin combination according to any one of claims 1 to 7, plasticizer D is Polyester, benzene
The plasticizer of formic acid system or phthalic acid ester system.
9. a kind of manufacturing method of the protective layer used resin combination of transfer paper is any one institute in manufacturing claims 1~8
The method of the protective layer used resin combination of the transfer paper stated,
Acrylic acid series polymeric compounds A, the kinematic viscosity measured at 25 DEG C according to the method for ASTM D445 are mixed in 1.5mm2/s
At least one kind of solvent B1 and plasticizer D of cycloalkanes series solvent and isoparaffin series solvent below.
10. the manufacturing method of the protective layer used resin combination of transfer paper according to claim 9, goes back mixture foam killer C.
11. a kind of laminated body, it is sequentially laminated with base stock, W Sol P layer, printing ink layer, any in claim 1~8
The protective layer that the dried object of the protective layer used resin combination of transfer paper described in one is constituted.
12. a kind of decoration transfer paper, is made of the laminated body described in claim 11.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2017007245 | 2017-01-19 | ||
| JP2017-007245 | 2017-01-19 | ||
| PCT/JP2018/001378 WO2018135579A1 (en) | 2017-01-19 | 2018-01-18 | Resin composition for transfer paper protective layers, method for producing same, laminate and transfer paper for painting |
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| CN110099799B CN110099799B (en) | 2020-12-11 |
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| CN114277611A (en) * | 2021-12-31 | 2022-04-05 | 佛山荷韵特种材料有限公司 | Special explosion-proof flower cover oil for ceramic stained paper, production process of special explosion-proof flower cover oil and ceramic stained paper |
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| JP7063262B2 (en) | 2022-05-09 |
| JPWO2018135579A1 (en) | 2019-11-07 |
| CN110099799B (en) | 2020-12-11 |
| WO2018135579A1 (en) | 2018-07-26 |
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