CN111886139A - Resin composition for transfer paper and laminate - Google Patents
Resin composition for transfer paper and laminate Download PDFInfo
- Publication number
- CN111886139A CN111886139A CN201980021023.1A CN201980021023A CN111886139A CN 111886139 A CN111886139 A CN 111886139A CN 201980021023 A CN201980021023 A CN 201980021023A CN 111886139 A CN111886139 A CN 111886139A
- Authority
- CN
- China
- Prior art keywords
- resin composition
- residue
- transfer paper
- acid
- glycol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- 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
- B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
- B32B7/04—Interconnection of layers
- B32B7/10—Interconnection of layers at least one layer having inter-reactive properties
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
Abstract
Provides a resinThe resin composition is suitably used as a composition for forming a film layer having good tensile properties and used for a blank for a picture such as a ceramic ware, and a laminate using the resin composition. Specifically disclosed is a resin composition for transfer paper, which contains a polymer (X) containing an alkyl (meth) acrylate as an essential raw material and B- (G-A), and a laminate having a film layer formed from a dried product of the resin compositionnAn ester compound (Y) represented by G-B (1) (wherein B represents a residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms, G represents a residue of an alkylene glycol having 2 to 12 carbon atoms or a residue of an oxyalkylene glycol having 4 to 12 carbon atoms, A represents a residue of a dicarboxylic acid, n represents a repeating number and is an integer of 0 to 30, G and A may be the same or different in each repeating, and a plurality of B and G present in the formula may be the same or different).
Description
Technical Field
The present invention relates to a resin composition which can be suitably used as a composition for forming a film layer having good tensile properties and used for a picture blank of a ceramic ware or the like, and a laminate using the resin composition.
Background
Conventionally, a single-sheet picture blank method (japanese: input method) using a transfer paper in which a liner paper, a water-soluble paste layer, an ink layer printed in a desired pattern, and a film layer are sequentially stacked has been widely used for picture blanks of plastic, wood, metal, porcelain, glass, enamel, ceramic tile, other ceramics, and the like (hereinafter referred to as "porcelain etc.). In this method, a transfer paper is immersed in water or warm water, a film layer with an ink layer is peeled off from a backing paper, slide transfer is performed at a predetermined position of a pottery or the like so that the ink layer is inside, moisture, air bubbles, and the like between the pottery or the like and the film layer are removed and dried, and then only the film layer is peeled off or baked to apply the ink layer to the surface of the pottery or the like, thereby fixing a pattern to the pottery or the like.
Examples of the resin used for the film layer include acrylic resins, vinyl acetate resins, alkyd resins, polyester resins, and cellulose resins, and particularly, acrylic resins are suitably used. Acrylic resins have a wide range of glass transition temperatures and molecular weights because they are freely available due to the abundant variety of raw material monomers and can be optionally copolymerized, and thus can adjust printing suitability (viscosity, solid content, solvent composition, and the like at the time of coating), coating film properties (balance between strength and elongation of a film layer, presence or absence of adhesiveness, and the like), and the like.
In general, plasticizers are used for the film layer and the ink layer of the transfer paper in order to balance strength and flexibility, and for example, phthalate plasticizers such as dialkyl phthalates including dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, diisononyl phthalate, diisodecyl phthalate, and the like, and alkyl benzyl phthalates including butyl benzyl phthalate, and the like are suitably used (for example, see patent document 1).
However, when these plasticizers are used, the strength as a film layer is insufficient at the time of transfer to ceramics or the like, and the balance with flexibility is poor, so that breakage or cracking is likely to occur, and improvement is required. Further, in recent years, due to the restriction of REACH and the like, there has been an increasing demand for phthalate-free plasticizers that do not use phthalate ester compounds.
Documents of the prior art
Patent document
Patent document 1: japanese patent laid-open publication No. 2017-078128
Disclosure of Invention
Problems to be solved by the invention
An object of the present invention is to provide a resin composition which can be suitably used as a composition for forming a film layer having good tensile properties and used for a blank for a picture such as a ceramic ware, and a laminate using the resin composition.
Means for solving the problems
The present inventors have conducted intensive studies and, as a result, have found that the above-mentioned problems can be solved by using a resin composition obtained by combining a (meth) acrylic resin with a specific ester compound, and have completed the present invention.
That is, the present invention provides a resin composition for transfer paper, which is characterized by containing a polymer (X) containing an alkyl (meth) acrylate as an essential raw material and an ester compound (Y) represented by the following general formula (1),
B-(G-A)n-G-B (1)
(wherein B is a residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms, G is a residue of an alkylene glycol having 2 to 12 carbon atoms or a residue of an oxyalkylene glycol having 4 to 12 carbon atoms, A is a residue of a dicarboxylic acid, n is a repeating number and is an integer of 0 to 30, and G and A may be the same or different in each repetition, and a plurality of B and G present in the formula may be the same or different.).
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a (meth) acrylic resin composition containing a specific plasticizer can be provided which is excellent in the balance between strength and flexibility when formed into a film without using a phthalate ester compound. The resin composition is a resin composition for transfer paper. The transfer paper (laminate) can be suitably used as a transfer paper (laminate) used for surface painting of ceramics or the like by a single-sheet painting method.
Detailed Description
The polymer (X) used in the present invention is a polymer using an alkyl (meth) acrylate as an essential raw material, and specific examples thereof include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, sec-butyl (meth) acrylate, cyclohexyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate, and these may be used alone or in combination of two or more.
Among these, from the viewpoint of excellent balance between flexibility and strength when forming a film layer of transfer paper, a polymer obtained using an alkyl (meth) acrylate is preferable, and a polymer using an alkyl ester having an alkyl group with 1 to 12 carbon atoms as a monomer is particularly preferable.
The polymer (X) used in the present invention may be a copolymer with another copolymerizable monomer other than the alkyl (meth) acrylate. Examples of such other monomers include: α, β -monoethylenically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, itaconic acid, crotonic acid, and the like; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate; amino group-containing alkyl (meth) acrylates such as diethylaminoethyl (meth) acrylate and dimethylaminoethyl (meth) acrylate; aromatic monovinyl monomers such as styrene, vinyltoluene and α -methylstyrene; maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide; unsaturated carboxylic acid anhydrides such as maleic anhydride; unsaturated acids such as maleic acid; vinyl acetate, vinyl propionate, (meth) acrylonitrile, and the like, and a plurality of arbitrary monomers may be used in combination.
The glass transition temperature of the polymer (X) can be determined by the Fox equation, and is preferably 20 ℃ or higher from the viewpoint of good blocking resistance when the polymer (X) is formed into a film layer or when the polymer (X) is formed into a laminate (transfer paper), and is particularly preferably in the range of 30 to 70 ℃ from the viewpoint of better handling properties.
The weight average molecular weight of the polymer (X) used in the present invention is preferably in the range of 30,000 to 200,000, more preferably in the range of 50,000 to 170,000, from the viewpoint of obtaining a resin composition which is easy to form a strong film layer, has sufficient fluidity, and is also excellent in processability.
In the present invention, the weight average molecular weight (Mw) is a value measured by GPC and converted to polystyrene. The measurement conditions of GPC are as follows.
[ GPC measurement conditions ]
A measuring device: HLC-8220GPC, manufactured by Tosoh corporation "
Column: "HHR-H" (6.0 mmI.D.. times.4 cm) protective column manufactured by Tosoh corporation, "TSK-GELGMHHR-N" (7.8 mmI.D.. times.30 cm) manufactured by Tosoh corporation, "TSK-GEL GMHHR-N" (7.8 mmI.D.. times.30 cm) manufactured by Tosoh corporation and "TSK-GEL GMHHR-N" (7.8 mmI.D.. times.30 cm) manufactured by Tosoh corporation
A detector: ELSD (Ortec 'ELSD 2000')
Data processing: "GPC-8020 Model II data analysis version 4.30" manufactured by Tosoh corporation "
The measurement conditions were as follows: column temperature 40 deg.C
Tetrahydrofuran (THF) as developing solvent
Flow rate 1.0 ml/min
Sample preparation: a tetrahydrofuran solution (1.0 mass% in terms of solid content of the resin) was filtered through a microfilter to obtain a solution (5. mu.l).
Standard sample: based on the manual of measurement of the aforementioned "GPC-8020 Model II data analysis version 4.30", the following monodisperse polystyrene having a known molecular weight was used.
(monodisperse polystyrene)
"A-500" made by Tosoh corporation "
"A-1000" made by Tosoh corporation "
"A-2500" made by Tosoh corporation "
"A-5000" manufactured by Tosoh corporation "
"F-1" made by Tosoh corporation "
"F-2" made by Tosoh corporation "
"F-4" made by Tosoh corporation "
"F-10" made by Tosoh corporation "
"F-20" made by Tosoh corporation "
"F-40" made by Tosoh corporation "
"F-80" made by Tosoh corporation "
"F-128" made by Tosoh corporation "
F-288, Tosoh corporation "
"F-550" made by Tosoh corporation "
As a method for producing the polymer (X) used in the present invention, various polymerization methods such as casting polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, and anion polymerization can be used. In the production method, bulk polymerization or solution polymerization is preferable because a polymer with less contamination of fine foreign matters can be obtained. In the solution polymerization, a solution prepared by dissolving a mixture of raw materials in an aromatic hydrocarbon solvent such as toluene or ethylbenzene may be used. When the polymerization is carried out by bulk polymerization, the polymerization can be initiated by irradiating the polymer with ionizing radiation using free radicals generated by heating as in the conventional case.
As the initiator used for the above polymerization reaction, any initiator generally used for radical polymerization, for example, azo compounds such as azobisisobutyronitrile; and organic peroxides such as benzoyl peroxide, lauroyl peroxide, and tert-butyl peroxy-2-ethylhexanoate. In the polymerization, the solution polymerization is usually carried out at a high temperature of 90 ℃ or higher, and therefore, peroxides, azo initiators and the like having a 10-hour half-life temperature of 80 ℃ or higher and being soluble in the organic solvent used are preferable, and specific examples thereof include 1, 1-bis (t-butylperoxy) 3,3, 5-trimethylcyclohexane, cyclohexane peroxide, 2, 5-dimethyl-2, 5-bis (benzoylperoxy) hexane, 1-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile and the like. These initiators are used in an amount of 0.005 to 5% by mass.
When the polymer (X) used in the present invention is polymerized, a molecular weight modifier may be used as needed. As the molecular weight regulator, any molecular weight regulator usually used in radical polymerization can be used, and examples thereof include thiol compounds such as butyl mercaptan, octyl mercaptan, dodecyl mercaptan and 2-ethylhexyl thioglycolate, and particularly preferred examples thereof are. These molecular weight regulators are added in a concentration range in which the degree of polymerization can be controlled within the above range.
The ester compound (Y) used in the present invention is represented by the following general formula (1) and is characterized in that the terminal is blocked by a residue of an aromatic carboxylic acid.
B-(G-A)n-G-B (1)
(wherein B is a residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms, G is a residue of an alkylene glycol having 2 to 12 carbon atoms or a residue of an oxyalkylene glycol having 4 to 12 carbon atoms, A is a residue of a dicarboxylic acid, n is a repeating number and is an integer of 0 to 30, and G and A may be the same or different and a plurality of B and G present in the formula may be the same or different.)
By blocking the terminal with a residue of an aromatic monocarboxylic acid, a film layer which is excellent in compatibility with the polymer (X), i.e., transparency and suitable as a transfer paper can be formed.
The number average molecular weight (Mn) of the ester compound (Y) used in the present invention is preferably in the range of 200 to 3000, and particularly preferably in the range of 250 to 1500, from the viewpoints of compatibility with the polymer (X), plasticizing effect, suppression of bleeding during molding, and balance between strength and flexibility when formed into a film. From these viewpoints, n representing the number of repetitions is an integer of 0 to 30, and the average value thereof is preferably in the range of 0 to 5.
In the general formula (1), B is the residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms. The number of carbon atoms herein does not include the carbon atoms in the carboxyl group. The "residue" of the residue of the aromatic monocarboxylic acid means a group not containing a terminal hydrogen atom in the carboxyl group.
Examples of the aromatic monocarboxylic acid include benzoic acid, dimethylbenzoic acid, trimethylbenzoic acid, tetramethylbenzoic acid, ethylbenzoic acid, propylbenzoic acid, butylbenzoic acid, p-isopropylbenzoic acid, p-tert-butylbenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, ethoxybenzoic acid, propoxybenzoic acid, naphthoic acid, nicotinic acid, furoic acid, anisic acid, and the like, and among these, benzoic acid is preferred from the viewpoint that the ester compound (Y) of the present invention can be easily synthesized by the production method described later, from the viewpoint that raw material availability in industry is easy, from the viewpoint that the molding processability of the obtained resin composition, and from the viewpoint that the tensile properties when a laminate (transfer paper) is produced are more excellent.
G in the general formula (1) is a residue of an alkylene glycol having 2 to 12 carbon atoms or a residue of an oxyalkylene glycol having 4 to 12 carbon atoms as described above. The residue herein refers to a group obtained by removing a hydroxyl group of a diol.
Examples of the alkylene glycol having 2 to 12 carbon atoms include ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butylene glycol, 1, 3-butylene glycol, 2-methyl-1, 3-propylene glycol, 1, 4-butylene glycol, 1, 5-pentanediol, 2-dimethyl-1, 3-propanediol (neopentyl glycol), 2-diethyl-1, 3-propanediol (3, 3-dimethylolpentane), 2-n-butyl-2-ethyl-1, 3-propanediol (3, 3-dimethylolheptane), 3-methyl-1, 5-pentanediol, 1, 6-hexanediol, 2, 4-trimethyl-1, 3-pentanediol, 1, 6-hexanediol, 1, 3-pentanediol, 1, 3-propanediol, 2-ethyl-1, 3-hexanediol, 2-methyl-1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, 1, 12-dodecanediol, and the like. Of these, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 3-butanediol, and 2-methyl-1, 3-propanediol are preferable, and ethylene glycol and 1, 2-propanediol are more preferable, from the viewpoint of excellent compatibility with the polymer (X).
Examples of the oxyalkylene glycol having 4 to 12 carbon atoms include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, tripropylene glycol, and the like.
A in the general formula (1) is a residue of a dicarboxylic acid, and may be a residue of any of an aliphatic compound and an aromatic compound. Here, the meaning of the residue is the same as described above.
The dicarboxylic acid is preferably an alkylene dicarboxylic acid having 2 to 12 carbon atoms from the viewpoint of more easily exhibiting the effects of the present invention, and examples thereof include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, fumaric acid, 1, 2-dicarboxycyclohexane, 1, 2-dicarboxycyclohexene, and the like. Among these, succinic acid, adipic acid, and 1, 2-dicarboxycyclohexane are preferable, and adipic acid is particularly preferable, from the viewpoint of more easily obtaining a film layer excellent in tensile properties and the like.
Examples of the aromatic dicarboxylic acid include phthalic acid, terephthalic acid, isophthalic acid, 1, 4-naphthalenedicarboxylic acid, 2, 3-naphthalenedicarboxylic acid, 2, 6-naphthalenedicarboxylic acid, 2, 7-naphthalenedicarboxylic acid, and 1, 8-naphthalenedicarboxylic acid. Among these, phthalic acid, terephthalic acid and isophthalic acid are preferable, and phthalic acid is most preferable, from the viewpoint that a film layer having high strength can be obtained more easily.
The ester compound (Y) represented by the above general formula (1) can be obtained, for example, by the following method.
The method comprises the following steps: a method in which an aromatic monocarboxylic acid or an aromatic monocarboxylic acid derivative, a dicarboxylic acid and a diol constituting each residue of the general formula (1) are added at once to react with each other.
The method 2 comprises the following steps: a method in which a dicarboxylic acid constituting the residue of the general formula (1) and a diol are reacted under a condition that the hydroxyl equivalent is more than the carboxyl equivalent to obtain a compound having a hydroxyl group at the terminal of the main chain, and then the compound is reacted with an aromatic monocarboxylic acid or an aromatic monocarboxylic acid derivative.
The aromatic monocarboxylic acid, dicarboxylic acid and diol in the above methods 1 and 2 may be the same as the raw materials described above for the residue, and only one kind of compound may be used, or two or more kinds may be used in combination. The aromatic monocarboxylic acid derivative may be reacted with a diol to form an ester bond in the same manner as in the case of using the aromatic monocarboxylic acid, and examples thereof include an esterified product thereof and an acid chloride thereof.
In both methods 1 and 2, the raw materials can be produced by an esterification reaction at a temperature of, for example, 180 to 250 ℃ for 10 to 25 hours in the presence of an esterification catalyst used as needed. The conditions such as the temperature and time of the esterification reaction are not particularly limited and may be appropriately set.
Examples of the esterification catalyst include: titanium catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin-based catalysts such as dibutyltin oxide; and organic sulfonic acid catalysts such as p-toluenesulfonic acid.
The amount of the esterification catalyst used may be suitably set, and is usually preferably in the range of 0.001 to 0.1 part by mass relative to 100 parts by mass of the total amount of the raw materials.
The ester compound (Y) in the present invention varies depending on the number average molecular weight thereof, the combination of raw materials, and the like, and is usually liquid, solid, paste, or the like at ordinary temperature.
The acid value of the ester compound (Y) in the present invention is preferably 5 or less, more preferably 1 or less, from the viewpoint of better compatibility with the polymer (X). For the same reason, the hydroxyl value is preferably 50 or less, and more preferably 20 or less.
The content of the ester compound (Y) in the resin composition for transfer paper of the present invention depends on the molecular weight of the polymer (X) used, the glass transition temperature thereof, and the like, but is preferably 3 to 50 parts by mass, more preferably 5 to 30 parts by mass, and still more preferably 10 to 20 parts by mass, based on 100 parts by mass of the polymer (X), from the viewpoint that the resin composition has good moldability and is easily balanced with the tensile properties of the resulting film layer.
The resin composition for transfer paper of the present invention is preferably used for the production of transfer paper for picture blanks, and is applied to a printing ink layer by printing or the like, and when the resin composition is applied, the resin composition for transfer paper of the present invention is preferably diluted with various organic solvents to a solution having a viscosity of 500 to 5000mPa · s and a solid content of 20 to 60 mass%, and more preferably 500 to 3000mPa · s and 30 to 50 mass%. The viscosity of the resin composition was measured at 25 ℃ and 60rpm using a B-type viscometer.
Examples of the solvent include: aromatic solvents such as toluene, xylene, and ethylbenzene; acetate-based solvents such as ethyl acetate, n-butyl acetate, isobutyl acetate, n-propyl acetate, isopropyl acetate, and amyl acetate; ketone solvents such as methyl isobutyl ketone, methyl ethyl ketone, diisobutyl ketone, and acetone; alcohol solvents such as methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol, tert-butanol, and benzyl alcohol; glycol solvents such as ethylene glycol, diethylene glycol, triethylene glycol, and propylene glycol; glycol ether solvents such as ethylene glycol monoethyl ether and ethylene glycol monobutyl ether; acetate solvents such as methyl cellosolve acetate and methoxypropyl acetate; hydrocarbon solvents such as n-hexane, cyclohexane, methylcyclohexane, and heptane; naphtha solvents such as Solvesso100, Solvesso150, Solvesso200, Swazol (registered trademark) 1000, Swazol1500, Swazol1800, Izod 100, Izod 150, and the like; naphthenic solvents such as Exxsol D30 and Exxsol D40 available from exxonmobil corporation; isoparaffin solvents such as Isopar (registered trademark) E, Isopar G, Isopar H, Isopar L and Isopar M from exxonmobil corporation may be used alone or in combination of two or more.
The solvent also includes a solvent to be mixed with the polymer (X), the ester compound (Y), and other components used in combination as needed. Examples of such a solvent include cyclohexanone and isobutyl ketone used for dissolving polysiloxane described later, and mineral spirits used for dissolving a plasticizer. These solvents may be used alone in 1 kind or in combination of plural kinds.
Of these, from the viewpoint of avoiding scattering and tailing at the time of coating the resin composition by printing or the like, and from the viewpoint of solubility of the polymer (X), the naphtha-based solvent is preferable, and the Solvesso100, the Solvesso150, the Solvesso200, the Swazol 1000, the Swazol1500, and the Swazol1800 are more preferable, and the Solvesso100 and the Swazol 1000 are further preferable. Since the resin composition is usually applied by printing by screen printing, offset printing, or the like, a type having a high boiling point is preferable in view of evaporation rate, dissolving power, odor, or the like, and a naphthenic solvent, a solvent naphtha solvent, a solvent of cellosolve solvent, or the like is preferably used.
The resin composition of the present invention is preferably used in the production method of transfer paper and the process for drawing a blank using transfer paper, which have been widely used in the past, as described above, and has good releasability, prevents permeation of printing ink with time, and is excellent in film properties, blocking resistance, and printing suitability.
In the resin composition for transfer paper of the present invention, additives such as a plasticizer, a thixotropic agent, and a defoaming agent other than the ester compound (Y) of the present invention may be added to satisfy viscosity stability, flexibility, defoaming property, drying property, and the like at the time of coating in other printing and the like. By adding these additives to be added in an amount of not more than 15 parts by mass, preferably not more than 10 parts by mass, based on 100 parts by mass of the polymer (X) in total, the printability and the suitability for lamination become better.
When the film layer formed of the resin composition for transfer paper of the present invention is peeled and removed by the drawing method, the resin composition for transfer paper of the present invention can be coated by printing or the like to form a film layer, and defoaming property can be exhibited to improve film forming property by further mixing silica with the resin composition for transfer paper of the present invention. The silica is preferably powder silica, and examples thereof include fumed silica, precipitated silica, and calcined silica. Any one of these may be used alone or a plurality of them may be used in combination. The silica may be a surface-untreated silica or a silica having a surface subjected to hydrophobic treatment. The surface of the surface-untreated silica is generally hydrophilic. By performing the hydrophobization treatment, the dispersibility, wettability, and fluidity can be improved.
The hydrophobization treatment of the silica surface can be carried out by various methods, and examples thereof include a method of treating the silica surface with an organic silicon compound such as organochlorosilane, organoalkoxysilane, organodisilazane, organopolysiloxane, organohydrogenpolysiloxane, and the like.
The specific surface area (BET method) of the silica is preferably 50m2A value of at least one of,/g, more preferably 100 to 700m2A more preferable range is 150 to 500m2(ii) in terms of/g. The larger the specific surface area, the higher the defoaming performance and the higher the film forming property. The content of silica is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the polymer (X), from the viewpoints of more excellent defoaming property and film-forming property, a proper range of viscosity of the resin composition, and good workability.
When the method of removing a film layer formed from the resin composition for transfer paper of the present invention is used, a silicone is further used in combination with the resin composition for transfer paper of the present invention, whereby a good releasability from the ink layer can be exhibited. Examples of the polysiloxane include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyether-modified siloxane, and polyester-modified hydroxyl-containing polydimethylsiloxane. Any one of these may be used alone or a plurality of them may be used in combination. Among these, polyether-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane and polyether-modified siloxane are preferably used from the viewpoint of releasability from various ink layers and film-forming property.
The polysiloxane is preferably composed of a polysiloxane having a weight average molecular weight of 50 to 230 and a polysiloxane having a weight average molecular weight of 380 to 1500, from the viewpoint of further improving the balance between the releasability and the film-forming property. The content of the polysiloxane is preferably 0.01 to 10 parts by mass, more preferably 0.01 to 5 parts by mass, per 100 parts by mass of the polymer (X), from the viewpoint of further improving the balance between releasability and film-forming property.
The ester compound (Y) in the present invention has a function as a plasticizer for the polymer (X), but substances conventionally used as plasticizers may be used in combination as appropriate within a range not impairing the effects of the present invention. Examples of other plasticizers include: phosphoric acid esters such as triaryl phosphate esters, trialkyl phosphate esters, and alkylaryl phosphate esters such as tricresyl phosphate; aliphatic dibasic acid esters such as dibutyl adipate and dioctyl adipate; ether bond-containing compounds such as polyethylene glycol, polypropylene glycol and dibutyldiglycol adipate; a polyester-based compound; soybean oil compounds such as epoxidized soybean oil; and the like. Any one of these plasticizers may be used alone or a plurality of them may be used in combination.
As other additives to be mixed into the resin composition of the present invention, for example, additives such as a thixotropic agent may be contained in order to satisfy viscosity stability, flexibility, drying property, and the like at the time of coating in printing and the like. Examples of the thixotropic agent include fatty acid amide wax, castor oil, hydrogenated castor oil, and the like.
The method for producing the resin composition of the present invention is not particularly limited, and the following methods are preferred: the polymer (X) is added little by little while stirring a solvent in a stirring apparatus equipped with a stirrer, a condenser and a thermometer, and after confirming that the polymer (X) is dissolved, the ester compound (Y) and various additives used in combination with them are added.
The resin composition of the present invention can be used in transfer paper. For example, the resin composition of the present invention is used for forming the film layer in a transfer sheet including a laminate in which a liner sheet, a water-soluble paste layer, an ink layer, and a film layer are sequentially laminated.
As described above, the laminate of the present invention is a laminate in which a liner paper, a water-soluble paste layer, an ink layer, and a film layer are laminated in this order. The water-soluble paste layer is formed so as to cover the entire surface of the interleaving paper. An ink layer is locally formed on the water-soluble paste layer. The film layer is formed so as to cover the ink layer. A portion of the film layer may be in contact with the water-soluble paste layer.
As the interleaving paper, interleaving paper (japanese paper) having excellent water absorbability can be mentioned. Examples of the water-soluble paste for forming the water-soluble paste layer include starch, polyvinyl alcohol, and carboxymethyl cellulose. Examples of the ink layer include a heat-curable ink, a thermoplastic ink, and a UV-curable ink. When the laminate is used as a transfer paper for a picture blank, an ink layer is formed from a pattern to be transferred to a pottery or the like. The ink layer may be a single layer or a plurality of layers.
The film layer is formed from a dried product of the resin composition of the present invention, and contains the polymer (X), the ester compound (Y), and other additives such as polysiloxane, silica, and a plasticizer used in combination. Drying is sufficient if the solvent can be volatilized.
The laminate can be produced, for example, as follows: an ink layer is formed using an ink on a liner paper on which a water-soluble paste layer is formed by applying a water-soluble paste, and the resin composition of the present invention is applied thereon and dried to form a film layer.
When the laminate is used as a transfer paper for a blank drawing, the blank drawing can be performed, for example, as follows. First, the laminate is immersed in water or warm water to dissolve the water-soluble paste layer, and the film layer with the ink layer is peeled off from the liner paper. The ink layer-attached film layer is disposed at a predetermined position of a ceramic or the like so that the ceramic or the like is in contact with the ink layer. Then, after removing moisture, air bubbles, and the like between the film layer with the ink layer and the ceramic ware and the like, only the film layer is peeled off or baked. This causes the ink layer to remain on the surface of the pottery or the like, thereby making a picture blank.
Examples
The present invention is further specifically described below based on examples. In the examples, parts and% are by mass unless otherwise specified.
Synthesis example 1
In a reaction vessel, 900g (7.38 mol) of benzoic acid (Kalama corporation), 322g (4.24 mol) of 1, 2-propanediol (Asahi glass company Co., Ltd.), and 0.373g of tetraisopropyl titanate as an esterification catalyst were charged into a 2-liter four-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, and while stirring under a nitrogen stream, the temperature was gradually increased to 230 ℃ and the acid value was kept at 230 ℃ under continuous heating to 2 or less, and the water produced was continuously removed. After the reaction, unreacted propylene glycol was distilled off under reduced pressure at 230 to 200 ℃ to obtain 949g of an ester compound (Y-1) (acid value 0.02, viscosity 75 mPas (25 ℃ C.)).
Synthesis example 2
In a reaction vessel, 783g (6.42 mol) of benzoic acid (Kalama corporation), 374g (3.53 mol) of diethylene glycol (Mitsubishi chemical corporation) and 0.347g of tetraisopropyl titanate as an esterification catalyst were charged into a four-necked flask having an internal volume of 2 liters and equipped with a thermometer, a stirrer and a reflux condenser, and while stirring under a nitrogen stream, the temperature was gradually increased to 230 ℃ and the temperature was continuously heated at 230 ℃ until the acid value became 2 or less, thereby continuously removing the produced water. After the reaction, the unreacted diethylene glycol was distilled off under reduced pressure at 230 to 200 ℃ to obtain 943g of an ester compound (Y-2) (acid value 0.02, viscosity 77 mPas (25 ℃ C.)).
Synthesis example 3
In a reaction vessel, 780g (6.39 mol) of benzoic acid (Kalama corporation), 471g (3.51 mol) of dipropylene glycol (Asahi glass company Co., Ltd.), and 0.378g of tetraisopropyl titanate as an esterification catalyst were charged into a 2-liter four-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, and while stirring under a nitrogen stream, the temperature was gradually increased to 230 ℃ and the temperature was continuously increased at 230 ℃ until the acid value became 2 or less, thereby continuously removing the produced water. After the reaction, unreacted dipropylene glycol was distilled off under reduced pressure at 230 to 200 ℃ to obtain 957g of an ester compound (Y-3) (acid value 0.01, viscosity 140 mPas (25 ℃ C.)).
Synthesis example 4
In a reaction vessel, 327g (2.24 g) of adipic acid (manufactured by Asahi Kasei Chemicals Co., Ltd.), 401g (5.28 mol) of 1, 2-propanediol (manufactured by Asahi glass company Co., Ltd.), 545g (4.47 mol) of benzoic acid (manufactured by Kalama Co., Ltd.), and 0.120g of tetraisopropyl titanate as an esterification catalyst were charged into a 2-liter four-neck flask equipped with a thermometer, a stirrer, and a reflux condenser, and while stirring under a nitrogen stream, the temperature was gradually increased to 230 ℃ and the temperature was continuously increased at 230 ℃ until the acid value became 5 or less, thereby continuously removing the produced water. After the reaction, unreacted 1, 2-propanediol was distilled off under reduced pressure at 230 to 200 ℃ to obtain 988g of an ester compound (Y-4) (acid value 0.5, viscosity 672 mPas (25 ℃ C.)).
Examples 1 to 4
Using 100 parts by mass of DianalBR-117 manufactured by mitsubishi chemical corporation as the polymer (X) and the ester compound (Y) obtained in synthesis example 1 in the parts by mass shown in table 1, 150 parts by mass of an exxonmobil co: the Solvesso100 was stirred until uniform, thereby preparing a resin composition. The composition was formed into a film on a glass substrate using a 0.508mm dispenser, dried at 25 ℃ for 24 hours, and peeled off from the glass substrate to prepare a film for evaluation.
Comparative examples 1 to 2
In the examples, films were produced in the same manner as in the examples except that di (2-ethylhexyl) phthalate (sansocize DOP, manufactured by shin-shi chemical co.
< evaluation method of Membrane >
The tensile strength and elongation were measured by a tensile tester to evaluate the tensile strength and elongation. The results are shown in Table 1.
Measurement equipment: tensilon Universal Material testing machine manufactured by Orientec corporation "
Sample shape: 10mm × 60mm × 20 μm
Test speed is 10mm/min
Full load of 10N
20mm between the clamps
And (3) measuring atmosphere: the temperature is 23 ℃ and the humidity is 50%
It is shown that the higher the upper yield stress and the higher the value of the tensile strength, the more excellent the strength of the transfer paper. It was also shown that the greater the tensile elongation, the more excellent the flexibility of the transfer paper.
[ Table 1]
Claims (8)
1. A resin composition for transfer paper, characterized by comprising a polymer (X) essentially comprising an alkyl (meth) acrylate and an ester compound (Y) represented by the following general formula (1),
B-(G-A)n-G-B (1)
wherein B is a residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms, G is a residue of an alkylene glycol having 2 to 12 carbon atoms or a residue of an oxyalkylene glycol having 4 to 12 carbon atoms, A is a residue of a dicarboxylic acid, n is the number of repetitions and is an integer of 0 to 30, G and A are optionally the same or different in each repetition, and a plurality of B and G present in the formula are optionally the same or different.
2. The resin composition for transfer paper according to claim 1, wherein the number average molecular weight of the ester compound (Y) is in the range of 200 to 3000.
3. The resin composition for transfer paper according to claim 1 or 2, wherein B in the general formula (1) is a residue of benzoic acid, G is a residue of ethylene glycol, propylene glycol, diethylene glycol or dipropylene glycol, and a is a residue of adipic acid or phthalic acid.
4. The resin composition for transfer paper according to any one of claims 1 to 3, wherein the ester compound (Y) is contained in an amount of 3 to 50 parts by mass based on 100 parts by mass of the polymer (X).
5. The resin composition for transfer paper according to any one of claims 1 to 4, wherein the glass transition temperature of the polymer (X) is in the range of 30 to 70 ℃.
6. The resin composition for transfer paper according to any one of claims 1 to 5, further comprising a solvent and silica.
7. The resin composition for transfer paper according to any one of claims 1 to 6, further comprising a polysiloxane.
8. A laminate comprising a film layer, an ink layer, a water-soluble paste layer and an interleaf paper, which are formed from a dried product of the resin composition for transfer paper according to any one of claims 1 to 7, laminated in this order.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2018-054301 | 2018-03-22 | ||
| JP2018054301 | 2018-03-22 | ||
| PCT/JP2019/010504 WO2019181719A1 (en) | 2018-03-22 | 2019-03-14 | Resin composition for transfer paper and multilayer body |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111886139A true CN111886139A (en) | 2020-11-03 |
Family
ID=67987638
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201980021023.1A Pending CN111886139A (en) | 2018-03-22 | 2019-03-14 | Resin composition for transfer paper and laminate |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP6756416B2 (en) |
| CN (1) | CN111886139A (en) |
| WO (1) | WO2019181719A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135055A (en) * | 2021-03-31 | 2021-07-20 | 珠海天威新材料股份有限公司 | Pyrography transfer paper and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10268778A (en) * | 1997-03-25 | 1998-10-09 | Mitsubishi Paper Mills Ltd | Thermal transfer image receiver sheet |
| WO2004002752A1 (en) * | 2002-07-01 | 2004-01-08 | Dainippon Ink And Chemicals, Inc. | Hydraulic transfer film and process for producing hydraulic transfer product therewith |
| CN102775310A (en) * | 2012-08-06 | 2012-11-14 | 南京林业大学 | Synthesis method of dibasic alcohol bi-benzoate |
| CN105392816A (en) * | 2013-05-21 | 2016-03-09 | 艾斯特工业有限公司 | Heat resistant polyethylene terephthalate and a process for the preparation of the same |
| CN105873978A (en) * | 2014-01-02 | 2016-08-17 | 艾默罗德卡拉玛化学品公司 | Polyester plasticizers with benzoic acid end-caps |
| CN106985587A (en) * | 2015-10-21 | 2017-07-28 | 三菱化学株式会社 | The protective layer used resin combination of transfer paper, its manufacture method and decoration transfer paper |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6040395B2 (en) * | 1978-06-02 | 1985-09-10 | 三菱レイヨン株式会社 | Peelable transfer resin composition and transfer painting method |
| JP2747913B2 (en) * | 1988-09-16 | 1998-05-06 | 三菱レイヨン株式会社 | Transfer paper overcoat and baking coloring method |
| JP2002179814A (en) * | 2000-12-11 | 2002-06-26 | Toray Ind Inc | Polyester film and decorative film |
| JP2003183559A (en) * | 2001-12-13 | 2003-07-03 | Mitsubishi Rayon Co Ltd | Resin composition for easily releasable transfer paper |
| US8308886B2 (en) * | 2006-07-17 | 2012-11-13 | E I Du Pont De Nemours And Company | Donor elements and processes for thermal transfer of nanoparticle layers |
| TW201341487A (en) * | 2011-12-27 | 2013-10-16 | Taica Corp | Activator composition for water pressure transfer, a water pressure transfer method and a water pressure transfer article |
-
2019
- 2019-03-14 JP JP2020508287A patent/JP6756416B2/en active Active
- 2019-03-14 CN CN201980021023.1A patent/CN111886139A/en active Pending
- 2019-03-14 WO PCT/JP2019/010504 patent/WO2019181719A1/en active Application Filing
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH10268778A (en) * | 1997-03-25 | 1998-10-09 | Mitsubishi Paper Mills Ltd | Thermal transfer image receiver sheet |
| WO2004002752A1 (en) * | 2002-07-01 | 2004-01-08 | Dainippon Ink And Chemicals, Inc. | Hydraulic transfer film and process for producing hydraulic transfer product therewith |
| CN102775310A (en) * | 2012-08-06 | 2012-11-14 | 南京林业大学 | Synthesis method of dibasic alcohol bi-benzoate |
| CN105392816A (en) * | 2013-05-21 | 2016-03-09 | 艾斯特工业有限公司 | Heat resistant polyethylene terephthalate and a process for the preparation of the same |
| CN105873978A (en) * | 2014-01-02 | 2016-08-17 | 艾默罗德卡拉玛化学品公司 | Polyester plasticizers with benzoic acid end-caps |
| CN106985587A (en) * | 2015-10-21 | 2017-07-28 | 三菱化学株式会社 | The protective layer used resin combination of transfer paper, its manufacture method and decoration transfer paper |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113135055A (en) * | 2021-03-31 | 2021-07-20 | 珠海天威新材料股份有限公司 | Pyrography transfer paper and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019181719A1 (en) | 2019-09-26 |
| JPWO2019181719A1 (en) | 2020-10-22 |
| JP6756416B2 (en) | 2020-09-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107075341B (en) | Stripping film is with re-releasing additive and stripping film organopolysiloxane composition and stripping film | |
| CN103765313A (en) | Photosensitive alkali-soluble silicone resin composition | |
| TW200944557A (en) | Curable composition | |
| JP6058843B1 (en) | Method for producing acrylic silicone resin emulsion | |
| CN104245846A (en) | Polysiloxane composition having radical-crosslinkable group | |
| US10683434B2 (en) | Organocopolymer dispersions | |
| JP2016121350A (en) | Silica dispersion, and active energy ray-curable resin composition | |
| CN108409903B (en) | Resin, varnish composition, offset printing ink and printed matter | |
| KR101389291B1 (en) | Aqueous binders for coatings with improved gloss | |
| CN111886139A (en) | Resin composition for transfer paper and laminate | |
| TWI752104B (en) | Energy curable aqueous compositions and process for preparing coated substrates or articles by using the same | |
| WO2011000782A1 (en) | Radiation curable compositions | |
| CN106985587B (en) | Resin composition for protective layer of transfer paper, process for producing the same, and decorative transfer paper | |
| US11091579B2 (en) | Aqueous dispersions including polyester particles, photopolymerizable compositions, articles, and methods | |
| WO2015140112A1 (en) | Radiation curable compositions comprising inert resins | |
| ZA200600573B (en) | Water-dilutable alkyd resins, method for the production and the utilization thereof | |
| JP6639819B2 (en) | Surface conditioner for coating materials | |
| KR20220121240A (en) | Curable composition comprising multi-stage polymer | |
| CN105358607B (en) | The manufacturing method of the alkyd modified silicone acrylic copolymer of oxidative cure type | |
| CN111793211A (en) | Aqueous polyorganosiloxane hybrid resin dispersion | |
| JP5223667B2 (en) | Internally added release agent for epoxy resin | |
| WO2018135579A1 (en) | Resin composition for transfer paper protective layers, method for producing same, laminate and transfer paper for painting | |
| JP2018070742A (en) | Active energy ray-curable resin composition | |
| JP6058842B1 (en) | Method for producing acrylic silicone resin emulsion | |
| TW201700530A (en) | Water-soluble polyester resin having improved water resistance and chemical resistance, water-dispersible emulsion comprising the same, and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |