WO2019181719A1 - Resin composition for transfer paper and multilayer body - Google Patents

Resin composition for transfer paper and multilayer body Download PDF

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Publication number
WO2019181719A1
WO2019181719A1 PCT/JP2019/010504 JP2019010504W WO2019181719A1 WO 2019181719 A1 WO2019181719 A1 WO 2019181719A1 JP 2019010504 W JP2019010504 W JP 2019010504W WO 2019181719 A1 WO2019181719 A1 WO 2019181719A1
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WO
WIPO (PCT)
Prior art keywords
resin composition
residue
transfer paper
acid
glycol
Prior art date
Application number
PCT/JP2019/010504
Other languages
French (fr)
Japanese (ja)
Inventor
崇史 野口
寛樹 所
Original Assignee
Dic株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to CN201980021023.1A priority Critical patent/CN111886139A/en
Priority to JP2020508287A priority patent/JP6756416B2/en
Publication of WO2019181719A1 publication Critical patent/WO2019181719A1/en

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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

Definitions

  • the present invention relates to a resin composition that has good tensile properties and can be suitably used as a composition for forming a film layer used for painting on ceramics and the like, and a laminate using the resin composition. .
  • ceramics plastic, wood, metal, ceramics, glass, enamel, tiles, and other ceramics (hereinafter referred to as “ceramics”) are printed on a backing sheet, a water-soluble glue layer, and a desired pattern.
  • a single paper painting method using a transfer paper in which an ink layer and a film layer are laminated in this order is widely used.
  • the transfer paper is immersed in water or warm water, the film layer with the ink layer is peeled off from the mount, and the ink layer is slid and transferred to a predetermined position on the ceramic or the like. After removing moisture between the layers, air bubbles, and the like and drying, only the film layer is peeled off or baked to apply the ink layer to the surface of the ceramic or the like, thereby fixing the pattern design to the ceramic or the like.
  • the resin used for the film layer examples include acrylic resins, vinyl acetate resins, alkyd resins, polyester resins, and cellulose resins, and acrylic resins are particularly preferably used.
  • Acrylic resins are abundant in the types of raw material monomers and can be arbitrarily copolymerized, so a wide range of glass transition temperatures and molecular weight resins can be obtained freely, so printing suitability (viscosity viscosity, solid content, Solvent composition, etc.), coating film properties (balance of strength and elongation of film layer, presence / absence of adhesiveness, etc.) can be adjusted.
  • a plasticizer is used in the film layer and ink layer of transfer paper to balance strength and flexibility.
  • Phthalate ester plasticizers such as dialkyl phthalates such as diisodecyl acid and alkyl benzyl phthalates such as butyl benzyl phthalate are preferably used (see, for example, Patent Document 1).
  • the problem to be solved by the present invention is a resin composition that has good tensile properties and can be suitably used as a composition for forming a film layer used for painting on ceramics and the like, and the resin composition It is providing the laminated body using this.
  • the present invention relates to a polymer (X) having a (meth) acrylic acid alkyl ester as an essential raw material, and the following general formula (1): B- (GA) n -GB (1) Wherein B is a residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms, and G is a residue of an alkylene glycol having 2 to 12 carbon atoms or an oxyalkylene glycol having 4 to 12 carbon atoms.
  • a residue is a residue of a dicarboxylic acid
  • n is the number of repetitions and is an integer of 0 to 30
  • G and A may be the same or different for each repetition, and there are a plurality of them in the formula B and G may be the same or different.
  • the resin composition for transfer paper characterized by including the ester compound (Y) represented by these, and the laminated body which has this dry film as a film layer.
  • a (meth) acrylic resin composition containing a specific plasticizer having an excellent balance between strength and flexibility when formed as a film without using a phthalate ester compound is provided.
  • This resin composition is a resin composition for transfer paper, and can be suitably used as transfer paper (laminate) used when painting on the surface of ceramics or the like by a single paper painting method.
  • the polymer (X) used in the present invention is a polymer having a (meth) acrylic acid alkyl ester as an essential raw material. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) ) N-butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, Sec-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. These may be used alone or in combination of two or more.
  • a film layer for forming transfer paper when used, it is a polymer obtained by using (meth) acrylic acid alkyl ester from the viewpoint of an excellent balance between flexibility and strength.
  • a polymer obtained by using an alkyl ester having an alkyl group having 1 to 12 carbon atoms as a monomer is preferable.
  • the polymer (X) used in the present invention may be a copolymer with other copolymerizable monomers other than the (meth) acrylic acid alkyl ester.
  • examples of such other monomers include ⁇ , ⁇ -monoethylenically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, itaconic acid, and crotonic acid, and 2-hydroxyethyl (meth) acrylate.
  • (Meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.
  • Amino group-containing alkyl acrylate aromatic monovinyl monomers such as styrene, vinyltoluene and ⁇ -methylstyrene, maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, and unsaturated carboxylic acid anhydrides such as maleic anhydride , Unsaturated acids such as maleic acid, vinyl acetate, vinyl propionate, ( Data) acrylonitrile and the like, may be more combination of any of the monomers.
  • the glass transition temperature of the polymer (X) can be determined from the Fox equation, and is 20 because it has good blocking resistance when formed as a film layer or a laminate (transfer paper).
  • the temperature is preferably not lower than 0 ° C., and particularly preferably in the range of 30 to 70 ° C. from the viewpoint of better handling.
  • the weight average molecular weight of the polymer (X) used in the present invention is in the range of 30,000 to 200,000, it is easy to form a strong film layer, fluidity is sufficient, and workability is also improved. It is preferable because an excellent resin composition is obtained, and more preferably in the range of 50,000 to 170,000.
  • the weight average molecular weight (Mw) is a value in terms of polystyrene based on GPC measurement.
  • the measurement conditions for GPC are as follows.
  • the method for producing the polymer (X) used in the present invention for example, various polymerization methods such as cast polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, anionic polymerization and the like can be used.
  • various polymerization methods such as cast polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, anionic polymerization and the like can be used.
  • bulk polymerization and solution polymerization are preferable because a polymer with a small amount of minute foreign matters can be obtained.
  • solution polymerization a solution prepared by dissolving a mixture of raw materials in an aromatic hydrocarbon solvent such as toluene or ethylbenzene can be used.
  • the polymerization can be started by irradiation with free radicals generated by heating or ionizing radiation as is usually done.
  • any initiator generally used in radical polymerization can be used.
  • azo compounds such as azobisisobutylnitrile; benzoyl peroxide, lauroyl peroxide, t-butyl
  • An organic peroxide such as peroxy-2-ethylhexanoate is used.
  • solution polymerization is generally used, so that the 10-hour half-life temperature is 80 ° C. or higher and the peroxide is soluble in the organic solvent used.
  • azobis initiators are preferred.
  • 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, cyclohexane peroxide, 2,5-dimethyl-2,5-di ( Benzoylperoxy) hexane, 1,1-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile and the like can be mentioned.
  • These initiators are used in the range of 0.005 to 5% by mass.
  • a molecular weight modifier may be used as necessary.
  • the molecular weight regulator any one used in general radical polymerization is used, and for example, mercaptan compounds such as butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-ethylhexyl thioglycolate are particularly preferable. These molecular weight regulators are added in a concentration range such that the degree of polymerization is controlled within the above range.
  • the ester compound (Y) used in the present invention has the following general formula (1): B- (GA) n -GB (1) Wherein B is a residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms, and G is a residue of an alkylene glycol having 2 to 12 carbon atoms or an oxyalkylene glycol having 4 to 12 carbon atoms. A residue, A is a residue of a dicarboxylic acid, n is the number of repetitions and is an integer of 0 to 30, and G and A may be the same or different for each repetition, and there are a plurality of them in the formula B and G may be the same or different.) And the terminal is sealed with an aromatic carboxylic acid residue. By sealing the terminal with a residue of an aromatic monocarboxylic acid, a film layer excellent in compatibility with the polymer (X), that is, excellent in transparency and suitable as a transfer paper can be formed.
  • B is a residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms
  • the ester compound (Y) used in the present invention is several from the viewpoint of compatibility with the polymer (X), plasticizing effect, bleed suppression during molding, and balance between strength and flexibility when used as a film.
  • the average molecular weight (Mn) is preferably in the range of 200 to 3000, and particularly preferably in the range of 250 to 1500. From these points, n indicating the number of repetitions is an integer of 0 to 30, but the average value is preferably in the range of 0 to 5.
  • B in the general formula (1) is a residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms as described above.
  • the number of carbon atoms here does not include carbon atoms in the carboxy group.
  • the “residue” in the residue of an aromatic monocarboxylic acid refers to a substance that does not contain a terminal hydrogen atom in a carboxy group.
  • aromatic monocarboxylic acid examples include benzoic acid, dimethyl benzoic acid, trimethyl benzoic acid, tetramethyl benzoic acid, ethyl benzoic acid, propyl benzoic acid, butyl benzoic acid, cumic acid, para-tert-butyl benzoic acid, orthotoluyl. Acid, metatoluic acid, p-toluic acid, ethoxybenzoic acid, propoxybenzoic acid, naphthoic acid, nicotinic acid, furoic acid, anisic acid and the like.
  • ester compound (Y ) From the viewpoint of being able to synthesize, the availability of industrial raw materials, and the molding processability of the resulting resin composition and the tensile properties when made into a laminate (transfer paper), benzoic acid is preferred. .
  • G in the general formula (1) is, as described above, 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 residue here means the group except the hydroxyl group in glycol.
  • alkylene glycol having 2 to 12 carbon atoms examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl- 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propane Diol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6 -Hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl
  • ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, -Methyl-1,3-propanediol is preferred, and ethylene glycol and 1,2-propylene glycol are more preferred.
  • Examples of the oxyalkylene glycol having 4 to 12 carbon atoms include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol.
  • a in the general formula (1) is a residue of a dicarboxylic acid, and may be a residue of a dicarboxylic acid of either an aliphatic compound or an aromatic compound.
  • the meaning of the residue here 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 expressing the effects of the present invention.
  • oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid Maleic acid, fumaric acid, 1,2-dicarboxycyclohexane, 1,2-dicarboxycyclohexene and the like.
  • succinic acid, adipic acid, and 1,2-dicarboxycyclohexane are preferable, and adipic acid is particularly preferable from the viewpoint of easily obtaining a film layer having more excellent tensile properties.
  • aromatic dicarboxylic acid examples include phthalic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, and 2,7-naphthalenedicarboxylic acid. 1,8-naphthalenedicarboxylic acid and the like.
  • phthalic acid, terephthalic acid, and isophthalic acid are preferable, and phthalic acid is most preferable because a film layer with higher strength can be easily obtained.
  • the ester compound (Y) represented by the general formula (1) can be obtained, for example, by the method shown below.
  • Method 1 A method in which an aromatic monocarboxylic acid or an aromatic monocarboxylic acid derivative, a dicarboxylic acid and a glycol constituting each residue of the general formula (1) are charged together and reacted.
  • Method 2 A compound having a hydroxyl group at the end of the main chain is obtained by reacting the dicarboxylic acid constituting the residue of the general formula (1) with glycol under the condition that the equivalent of the hydroxyl group is larger than the equivalent of the carboxyl group. And then reacting the compound with an aromatic monocarboxylic acid or an aromatic monocarboxylic acid derivative.
  • the aromatic monocarboxylic acid, dicarboxylic acid and glycol in the above methods 1 and 2 are the same as the raw materials mentioned for the above-mentioned residues, and even if only a single compound is used, two or more kinds are used in combination. Also good.
  • the aromatic monocarboxylic acid derivative is not particularly limited as long as it can react with glycol to form an ester bond in the same manner as in the case of using the aromatic monocarboxylic acid, and examples thereof include esterified products, acid chlorides, and the like. Can be mentioned.
  • the raw material is produced by an esterification reaction in the presence of an esterification catalyst as necessary, for example, within a temperature range of 180 to 250 ° C. for 10 to 25 hours. be able to.
  • an esterification catalyst as necessary, for example, within a temperature range of 180 to 250 ° C. for 10 to 25 hours. be able to.
  • conditions, such as temperature of esterification reaction and time are not specifically limited, You may set suitably.
  • esterification catalyst examples include titanium catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin catalysts such as dibutyltin oxide; and organic sulfonic acid catalysts such as p-toluenesulfonic acid.
  • the amount of the esterification catalyst used may be set as appropriate, but usually it is preferably used in the range of 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of raw materials.
  • the properties of the ester compound (Y) in the present invention vary depending on factors such as the number average molecular weight and the combination of raw materials, but are usually liquid, solid, paste, etc. at room 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).
  • the hydroxyl value is preferably 50 or less, 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 and its glass transition temperature, the moldability as a resin composition is good. From the viewpoint that it is easy to balance with the tensile properties and the like of the obtained film layer, it is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymer (X). Part by mass is more preferable.
  • the resin composition for transfer paper of the present invention is preferably used for the production of a transfer paper for painting, and is applied on the printing ink layer by printing or the like. It is preferably diluted with an organic solvent to form a solution having a viscosity of 500 to 5000 mPa ⁇ s and a solid content of 20 to 60% by mass, and more preferably 500 to 3000 mPa ⁇ s and 30 to 50% by mass.
  • the viscosity of the resin composition is a value measured using a B-type viscometer at 25 ° C. and a rotation speed of 60 rpm.
  • the solvent examples include aromatic solvents such as toluene, xylene and ethylbenzene; acetate solvents such as ethyl acetate, normal butyl acetate, isobutyl acetate, normal propyl acetate, isopropyl acetate and amyl acetate; methyl isobutyl ketone, methyl ethyl ketone, Ketone solvents such as diisobutyl ketone and acetone; alcohol solvents such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol, normal butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, and benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, Glycol solvents such as propylene glycol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc.
  • aromatic solvents such as toluene, xylene and
  • Glycol ether solvents such as methyl cellosolve acetate and methoxypropyl acetate; hydrocarbon solvents such as normal hexane, cyclohexane, methylcyclohexane and heptane; Solvesso 100, Solvesso 150, Solvesso 200 from ExxonMobil Corporation , Naphtha solvents such as SWAZOL (registered trademark) 1000, SWAZOL 1500, SWAZOL 1800, IZUMO Kosan Co., Ltd., Ipsol 150, IPZOL 150, etc .; Naphthenic solvents; Isopar (registered trademark) E, Isopar G, Isopar H, Isopar L, Isopar M and other isoparaffinic solvents from ExxonMobil Corporation; It may be used in a mixture of two or more of them in Germany.
  • acetate solvents such as methyl cellosolve acetate and methoxypropyl a
  • the solvent includes a solvent blended with these components when blending the polymer (X), the ester compound (Y), and other components used in combination as necessary.
  • a solvent examples include cyclohexanone and isobutyl ketone used for dissolving polysiloxane described later, mineral spirit used for dissolving a plasticizer, and the like. Any one of these solvents may be used alone or in combination of two or more.
  • a naphtha solvent is preferable from the viewpoint of eliminating scattering and stringing when the resin composition is applied by printing or the like, and from the viewpoint of solubility of the polymer (X), and Solvesso 100, Solvesso 150, Solvesso 200. , Swazol 1000, Swazol 1500, and Swazole 1800 are more preferable, and Solvesso 100 and Swazol 1000 are more preferable. Since the resin composition is usually printed and applied by screen printing, flat printing, etc., in consideration of evaporation rate, dissolving power, odor, etc., those having a relatively high boiling point are preferred. Naphthenic solvents, solvent naphtha solvents, cellosolve solvents A solvent or the like is preferably used.
  • the resin composition of the present invention is preferably applied to a transfer paper preparation method widely used in the past as described above and a painting method using the transfer paper, and has a good releasability, and the aging of the printing ink.
  • the film has excellent physical properties, anti-blocking properties and printability.
  • the resin composition for transfer paper of the present invention satisfies the viscosity stability, flexibility, antifoaming property, drying property, etc. at the time of application in other printing.
  • Auxiliaries such as plasticizers, thixotropic agents and antifoaming agents can be added. These added auxiliaries are added in an amount not exceeding 15 parts by mass, and preferably not exceeding 10 parts by mass, with respect to 100 parts by mass of the polymer (X) in terms of the total amount. It becomes good.
  • silica is preferably powdered silica, and examples thereof include fumed silica, precipitated silica, and fired silica. Any of these may be used alone or in combination of two or more.
  • the surface untreated silica may be sufficient and the silica by which the surface was hydrophobized may be sufficient.
  • the surface of the untreated silica is usually hydrophilic.
  • Hydrophobic treatment of the silica surface can be performed by various methods, for example, a method of treating the silica surface with an organosilicon compound such as organochlorosilane, organoalkoxysilane, organodisilazane, organopolysiloxane, organohydrogenpolysiloxane, etc. Is mentioned.
  • organosilicon compound such as organochlorosilane, organoalkoxysilane, organodisilazane, organopolysiloxane, organohydrogenpolysiloxane, etc. Is mentioned.
  • the specific surface area (BET method) of the silica is preferably 50 m 2 / g or more, more preferably 100 to 700 m 2 / g, and even more preferably 150 to 500 m 2 / g.
  • the larger the specific surface area the better the defoaming performance and the better the film formability.
  • content of silica it is excellent in defoaming property and film-forming property, and the viscosity of the resin composition is in an appropriate range, and the workability is good, so that the polymer (X) is 100 parts by mass. 0.001 to 10 parts by mass is preferable, and 0.01 to 5 parts by mass is more preferable.
  • polysiloxane in combination with the resin composition for transfer paper of the present invention. Good peelability from the layer can be developed.
  • the polysiloxane include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyether-modified siloxane, and polyester-modified hydroxyl group-containing polydimethylsiloxane.
  • polyether-modified polydimethylsiloxane aralkyl-modified polymethylalkylsiloxane, and polyether-modified siloxane are preferably used from the viewpoints of peelability from various ink layers and film formability.
  • the polysiloxane is 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 a better balance between peelability and film formability. Is preferred.
  • the content of the polysiloxane is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymer (X) from the viewpoint of a better balance between peelability and film formability, and 0.01 to 5 parts. Part by mass is more preferable.
  • the ester compound (Y) in the present invention has a function as a plasticizer of the polymer (X), but those conventionally used as a plasticizer are appropriately used in a range not impairing the effects of the present invention. You may do it.
  • plasticizers include phosphate esters such as triaryl phosphates such as tricresyl phosphate, trialkyl phosphates and alkylaryl phosphates; aliphatic dibasic acids such as dibutyl adipate and dioctyl adipate Examples include esters; compounds containing ether bonds such as polyethylene glycol, polypropylene glycol, dibutyl glycol adipate; polyester compounds; soybean oil compounds such as epoxidized soybean oil; These plasticizers can be used alone or in combination of two or more.
  • an auxiliary agent such as a thixotropic agent is included in order to satisfy viscosity stability, flexibility, drying property, etc. at the time of application in printing or the like. be able to.
  • the thixotropic agent include fatty acid amide wax, 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.
  • a solvent is charged into a stirrer equipped with a stirrer, a cooling tube, and a thermometer, and the polymer (X) is slightly added while stirring this.
  • a method of adding the ester compound (Y) and other various additives that are used in combination after adding the polymer (X) and confirming that the polymer (X) is dissolved is preferable.
  • the resin composition of the present invention is used for transfer paper.
  • the resin composition of the present invention is used to form the film layer of transfer paper comprising a laminate in which a backing paper, a water-soluble paste layer, an ink layer, and a film layer are laminated in this order.
  • the laminate of the present invention is a laminate in which, for example, a mount, 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 mount.
  • the ink layer is partially formed on the water-soluble paste layer.
  • the film layer is formed so as to cover the ink layer. Part of the film layer may be in contact with the water-soluble paste layer
  • Examples of the mount include a mount (Japanese paper) having good water absorption.
  • Examples of the water-soluble paste forming the water-soluble paste layer include starch, polyvinyl alcohol, carboxymethyl cellulose and the like.
  • Examples of the ink layer include thermosetting ink, thermoplastic ink, and UV curable ink. When the laminate is used as a transfer sheet for painting, the ink layer is formed with a pattern transferred to a ceramic or the like.
  • the ink layer may be a single layer or a multilayer.
  • the film layer is composed of a dried product of the above-described resin composition of the present invention.
  • the polymer (X), the ester compound (Y), and other used in combination, such as polysiloxane, silica, and plasticizer Additives are included.
  • the drying is not limited as long as the solvent can be volatilized.
  • the laminate is formed, for example, by forming an ink layer using ink on a mount on which a water-soluble paste layer is applied to form a water-soluble paste layer, and the resin composition of the present invention is applied thereon. It can be produced by drying to form a film layer.
  • the laminate When the laminate is used as a transfer paper for painting, for example, painting can be performed 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 mount. The film layer with the ink layer is disposed at a predetermined position of the ceramic or the like so that the ceramic or the like and the ink layer are in contact with each other. And after removing the water
  • Synthesis example 1 In a reaction vessel, 900 g (7.38 mol) of benzoic acid (manufactured by Kalama), 322 g (4.24 mol) of 1,2-propylene glycol (manufactured by Asahi Glass Co., Ltd.), and 0.373 g of tetraisopropyl titanate as an esterification catalyst. , Charged in a 2 liter four-necked flask equipped with a thermometer, stirrer, and reflux condenser and gradually heated to 230 ° C. while stirring under a nitrogen stream, resulting in an acid value of 2 or less Heating at 230 ° C. was continued until water formed was continuously removed.
  • ester compound (Y-1) (acid value 0.02, viscosity 75 mPa ⁇ s (25 ° C.)).
  • Synthesis example 2 In a reaction vessel, 783 g (6.42 mol) of benzoic acid (manufactured by Kalama), 374 g (3.53 mol) of diethylene glycol (manufactured by Mitsubishi Chemical Corporation), 0.347 g of tetraisopropyl titanate as an esterification catalyst, A four-necked flask with an internal volume of 2 liters equipped with a stirrer and a reflux condenser was charged stepwise to 230 ° C. while stirring under a nitrogen stream, and at 230 ° C. until the acid value became 2 or less. Heating was continued and water formed was continuously removed.
  • ester compound (Y-2) (acid number 0.02, viscosity 77 mPa ⁇ s (25 ° C.)) was obtained by distilling off unreacted diethylene glycol at 230 to 200 ° C. under reduced pressure.
  • Synthesis example 3 In a reaction vessel, 780 g (6.39 mol) of benzoic acid (manufactured by Kalama), 471 g (3.51 mol) of dipropylene glycol (manufactured by Asahi Glass Co., Ltd.), 0.378 g of tetraisopropyl titanate as an esterification catalyst, a thermometer , Charged in a two-liter four-necked flask equipped with a stirrer and a reflux condenser, gradually heated to 230 ° C. while stirring under a nitrogen stream, and 230 ° C. until the acid value became 2 or less. And the water produced was continuously removed.
  • Synthesis example 4 In a reaction vessel, adipic acid (Asahi Kasei Chemicals) 327 g (2.24), 1,2-propylene glycol (Asahi Glass Co., Ltd.) 401 g (5.28 mol), benzoic acid (Kalama Co., Ltd.) 545 g (4. 47 mol), 0.120 g of tetraisopropyl titanate as an esterification catalyst was charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and stirred at 230 ° C. under a nitrogen stream.
  • ester compound (Y-4) (acid value 0.5, viscosity 672 mPa ⁇ s (25 ° C.)). Obtained.
  • Examples 1 to 4 As the polymer (X), 100 parts by mass of Dainal BR-117 manufactured by Mitsubishi Chemical Corporation and the ester compound (Y) obtained in Synthesis Example 1 were used in the parts by mass shown in Table 1, and further a solvent. As ExxonMobil Co., Ltd .: Solvesso 100 was stirred and mixed uniformly in 150 parts by mass to prepare a resin composition. This composition was formed into a film on a glass substrate using a 0.508 mm applicator, dried at 25 ° C. for 24 hours, and then peeled off from the glass substrate to prepare an evaluation film.

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Abstract

Provided are: a resin composition which has good tensile characteristics and is suitable for use as a composition that forms a film layer that is used for painting of pottery and porcelain products and the like; and a multilayer body which uses this resin composition. Specifically provided are: a resin composition for transfer paper, which contains a polymer (X) that uses an alkyl (meth)acrylate ester as an essential starting material and an ester compound (Y) that is represented by formula (1) B-(G-A)n-G-B (wherein B represents a residue of an aromatic monocarboxylic acid having 6-12 carbon atoms; G represents a residue of an alkylene glycol having 2-12 carbon atoms or a residue of an oxyalkylene glycol having 4-12 carbon atoms; A represents a residue of a dicarboxylic acid; n represents the number of repetition, which is an integer of 0-30; G and A may be the same as or different from each other in each repeating unit; and the plurality of the B moieties and the plurality of the G moieties in the formula may be the same as or different from each other, respectively); and a multilayer body which has a film layer that is formed of a dried product of this resin composition.

Description

転写紙用樹脂組成物及び積層体Resin composition for transfer paper and laminate
　本発明は、引張特性が良好であり、陶磁器等の絵付けの際に使用するフィルム層を形成する組成物として好適に用いることができる樹脂組成物と、該樹脂組成物を用いた積層体に関する。 The present invention relates to a resin composition that has good tensile properties and can be suitably used as a composition for forming a film layer used for painting on ceramics and the like, and a laminate using the resin composition. .
　従来、プラスチック、木、金属、陶磁器、ガラス、ホーロー、タイル、その他セラミック等（以下、「陶磁器等」という。）の絵付けには、台紙と水溶性糊剤層と所望の模様絵柄に印刷されたインキ層とフィルム層とがこの順に積層した転写紙を用いる単紙絵付法が広く用いられている。この方法では、転写紙を水または温水に浸漬し、台紙よりインキ層の付いたフィルム層を剥離し、陶磁器等の所定の位置にインキ層が内側になるようにスライド転写し、陶磁器等とフィルム層の間の水分、気泡等を除去し、乾燥した後、フィルム層のみを剥離するもしくは焼成することによって、インキ層を陶磁器等の表面に施すことにより模様絵柄を陶磁器等に固定させる。 Traditionally, plastic, wood, metal, ceramics, glass, enamel, tiles, and other ceramics (hereinafter referred to as “ceramics”) are printed on a backing sheet, a water-soluble glue layer, and a desired pattern. A single paper painting method using a transfer paper in which an ink layer and a film layer are laminated in this order is widely used. In this method, the transfer paper is immersed in water or warm water, the film layer with the ink layer is peeled off from the mount, and the ink layer is slid and transferred to a predetermined position on the ceramic or the like. After removing moisture between the layers, air bubbles, and the like and drying, only the film layer is peeled off or baked to apply the ink layer to the surface of the ceramic or the like, thereby fixing the pattern design to the ceramic or the like.
　上記フィルム層に使用される樹脂としては、アクリル系樹脂、酢酸ビニル樹脂、アルキッド樹脂、ポリエステル樹脂、セルロース系樹脂等があり、特にアクリル系樹脂が好適に用いられている。アクリル系樹脂は、原料のモノマーの種類が豊富で、かつ任意に共重合できるため、広範囲のガラス転移温度や分子量の樹脂が自由に得られることから、印刷適性（塗布時の粘度、固形分、溶剤組成等）、塗膜物性（フィルム層の強度と伸度のバランス及び粘着性の有無等）等の調整が可能である。 Examples of the resin used for the film layer include acrylic resins, vinyl acetate resins, alkyd resins, polyester resins, and cellulose resins, and acrylic resins are particularly preferably used. Acrylic resins are abundant in the types of raw material monomers and can be arbitrarily copolymerized, so a wide range of glass transition temperatures and molecular weight resins can be obtained freely, so printing suitability (viscosity viscosity, solid content, Solvent composition, etc.), coating film properties (balance of strength and elongation of film layer, presence / absence of adhesiveness, etc.) can be adjusted.
　一般に、転写紙のフィルム層及びインキ層には、強度と柔軟性のバランスをとるために可塑剤が使用されており、例えば、フタル酸ジブチル、フタル酸ジヘキシル、フタル酸ジオクチル、フタル酸ジイソノニル、フタル酸ジイソデシル等のフタル酸ジアルキルエステル、フタル酸ブチルベンジル等のフタル酸アルキルベンジルなど、フタル酸エステル系可塑剤が好適に使用されている（例えば、特許文献１参照）。 Generally, a plasticizer is used in the film layer and ink layer of transfer paper to balance strength and flexibility. For example, dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, diisononyl phthalate, phthalate Phthalate ester plasticizers such as dialkyl phthalates such as diisodecyl acid and alkyl benzyl phthalates such as butyl benzyl phthalate are preferably used (see, for example, Patent Document 1).
　しかし、これらの可塑剤を用いた場合、陶磁器等へ転写する際のフィルム層としての強度が不足し、また柔軟性とのバランスにかけており、破断や割れが発生しやすく、改良が求められている。さらに近年、ＲＥＡＣＨ等の規制により、フタル酸エステル系化合物を使用しないフタル酸エステルフリーの可塑剤要求が高まっている。 However, when these plasticizers are used, the strength as a film layer at the time of transferring to ceramics, etc. is insufficient, and the balance with flexibility is easily generated, and breakage and cracking are likely to occur, and improvement is required. . Furthermore, in recent years, due to regulations such as REACH, there has been an increasing demand for plasticizers free of phthalate esters that do not use phthalate-based compounds.
特開２０１７－０７８１２８号公報Japanese Unexamined Patent Publication No. 2017-078128
　本発明が解決しようとする課題は、引張特性が良好であり、陶磁器等の絵付けの際に使用するフィルム層を形成する組成物として好適に用いることができる樹脂組成物と、該樹脂組成物を用いた積層体を提供することにある。 The problem to be solved by the present invention is a resin composition that has good tensile properties and can be suitably used as a composition for forming a film layer used for painting on ceramics and the like, and the resin composition It is providing the laminated body using this.
　本発明者らは鋭意検討を行った結果、（メタ）アクリル系樹脂に特定のエステル化合物を組み合わせてなる樹脂組成物を用いることにより、前記課題が解決できることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that the above problems can be solved by using a resin composition obtained by combining a specific ester compound with a (meth) acrylic resin, and have completed the present invention. It was.
　即ち、本発明は、（メタ）アクリル酸アルキルエステルを必須の原料とする重合体（Ｘ）と、下記一般式（１）
　Ｂ－（Ｇ－Ａ）ｎ－Ｇ－Ｂ　　　　（１）
　（式中、Ｂは炭素原子数６～１２の芳香族モノカルボン酸の残基であり、Ｇは炭素原子数２～１２のアルキレングリコールの残基または炭素原子数４～１２のオキシアルキレングリコールの残基であり、Ａはジカルボン酸の残基であり、ｎは繰り返し数であって０～３０の整数であり、繰り返しごとにＧ及びＡは同一でも異なっていてもよく、式中に複数あるＢ及びＧは同一でも異なっていても良い。）
で表されるエステル化合物（Ｙ）とを含有することを特徴とする転写紙用樹脂組成物、及びこれの乾燥膜をフィルム層として有する積層体を提供するものである。 That is, the present invention relates to a polymer (X) having a (meth) acrylic acid alkyl ester as an essential raw material, and the following general formula (1):
B- (GA) n -GB (1)
Wherein B is a residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms, and G is a residue of an alkylene glycol having 2 to 12 carbon atoms or an oxyalkylene glycol having 4 to 12 carbon atoms. A residue, A is a residue of a dicarboxylic acid, n is the number of repetitions and is an integer of 0 to 30, and G and A may be the same or different for each repetition, and there are a plurality of them in the formula B and G may be the same or different.)
The resin composition for transfer paper characterized by including the ester compound (Y) represented by these, and the laminated body which has this dry film as a film layer.
　本発明によれば、フタル酸エステル系化合物を使用しなくても、フィルムとして成形した際の強度と柔軟性とのバランスに優れた、特定の可塑剤を含む（メタ）アクリル系樹脂組成物を提供することができる。この樹脂組成物は、転写紙用の樹脂組成物であって、陶磁器等への表面に単紙絵付法にて絵付けする際に用いる転写紙（積層体）として好適に用いることができる。 According to the present invention, a (meth) acrylic resin composition containing a specific plasticizer having an excellent balance between strength and flexibility when formed as a film without using a phthalate ester compound is provided. Can be provided. This resin composition is a resin composition for transfer paper, and can be suitably used as transfer paper (laminate) used when painting on the surface of ceramics or the like by a single paper painting method.
　本発明で用いる重合体（Ｘ）は、（メタ）アクリル酸アルキルエステルを必須の原料とする重合体であり、具体的には、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ－ブチル、（メタ）アクリル酸イソブチル、（メタ）アクリル酸ｔ－ブチル、（メタ）アクリル酸Ｓｅｃ－ブチル、（メタ）アクリル酸シクロヘキシル、（メタ）アクリル酸２－エチルヘキシル等が挙げられ、単独でも２種以上を併用しても良い。 The polymer (X) used in the present invention is a polymer having a (meth) acrylic acid alkyl ester as an essential raw material. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) ) N-butyl acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, Sec-butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, etc. These may be used alone or in combination of two or more.
　これらの中でも、転写紙を形成するフィルム層とした際に、柔軟性と強度とのバランスに優れたものとなる観点から、（メタ）アクリル酸アルキルエステルを用いて得られる重合体であることが好ましく、特にアルキル基の炭素数が１～１２のアルキルエステルを単量体として用いてなる重合体であることが好ましい。 Among these, when a film layer for forming transfer paper is used, it is a polymer obtained by using (meth) acrylic acid alkyl ester from the viewpoint of an excellent balance between flexibility and strength. In particular, a polymer obtained by using an alkyl ester having an alkyl group having 1 to 12 carbon atoms as a monomer is preferable.
　また、本発明で用いる重合体（Ｘ）は、（メタ）アクリル酸アルキルエステル以外の共重合可能な他の単量体との共重合体であっても良い。このような他の単量体としては、例えば、（メタ）アクリル酸、マレイン酸、イタコン酸、クロトン酸等のα，β－モノエチレン性不飽和カルボン酸、（メタ）アクリル酸２－ヒドロキシエチル、（メタ）アクリル酸２－ヒドロキシプロピル、（メタ）アクリル酸４－ヒドロキシブチル等の（メタ）アクリル酸ヒドロキシアルキル、（メタ）アクリル酸ジエチルアミノエチル、（メタ）アクリル酸ジメチルアミノエチル等の（メタ）アクリル酸アミノ基含有アルキル、スチレン、ビニルトルエン、α－メチルスチレン等の芳香族モノビニルモノマー、Ｎ－フェニルマレイミド、Ｎ－シクロヘキシルマレイミド等のマレイミド類、無水マレイン酸等の不飽和カルボン酸無水物類、マレイン酸等の不飽和酸類、酢酸ビニル、プロピオン酸ビニル、（メタ）アクリロニトリル等が挙げられ、任意の単量体を複数併用しても良い。 Further, the polymer (X) used in the present invention may be a copolymer with other copolymerizable monomers other than the (meth) acrylic acid alkyl ester. Examples of such other monomers include α, β-monoethylenically unsaturated carboxylic acids such as (meth) acrylic acid, maleic acid, itaconic acid, and crotonic acid, and 2-hydroxyethyl (meth) acrylate. (Meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc. ) Amino group-containing alkyl acrylate, aromatic monovinyl monomers such as styrene, vinyltoluene and α-methylstyrene, maleimides such as N-phenylmaleimide and N-cyclohexylmaleimide, and unsaturated carboxylic acid anhydrides such as maleic anhydride , Unsaturated acids such as maleic acid, vinyl acetate, vinyl propionate, ( Data) acrylonitrile and the like, may be more combination of any of the monomers.
　前記重合体（Ｘ）のガラス転移温度は、Ｆｏｘの式より求めることができ、フィルム層として成形した際、あるいは、積層体（転写紙）とした際の耐ブロッキング性が良好であることから２０℃以上であることが好ましく、特に３０～７０℃の範囲であることが取り扱いがより良好となる観点から好ましいものである。 The glass transition temperature of the polymer (X) can be determined from the Fox equation, and is 20 because it has good blocking resistance when formed as a film layer or a laminate (transfer paper). The temperature is preferably not lower than 0 ° C., and particularly preferably in the range of 30 to 70 ° C. from the viewpoint of better handling.
　本発明で用いる重合体（Ｘ）の重量平均分子量は、３０，０００～２００，０００の範囲であることが、強度のあるフィルム層を形成しやすく、且つ流動性が十分で、加工性にも優れる樹脂組成物が得られることから好ましく、５０，０００～１７０，０００の範囲であることがより好ましい。 The weight average molecular weight of the polymer (X) used in the present invention is in the range of 30,000 to 200,000, it is easy to form a strong film layer, fluidity is sufficient, and workability is also improved. It is preferable because an excellent resin composition is obtained, and more preferably in the range of 50,000 to 170,000.
　ここで、本発明において、重量平均分子量（Ｍｗ）はＧＰＣ測定に基づきポリスチレン換算した値である。なお、ＧＰＣの測定条件は以下の通りである。 Here, in the present invention, the weight average molecular weight (Mw) is a value in terms of polystyrene based on GPC measurement. The measurement conditions for GPC are as follows.
　［ＧＰＣ測定条件］
　測定装置：東ソー株式会社製「ＨＬＣ－８２２０　ＧＰＣ」
　カラム：東ソー株式会社製ガードカラム「ＨＨＲ－Ｈ」（６．０ｍｍＩ．Ｄ．×４ｃｍ）＋東ソー株式会社製「ＴＳＫ－ＧＥＬ　ＧＭＨＨＲ－Ｎ」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）＋東ソー株式会社製「ＴＳＫ－ＧＥＬ　ＧＭＨＨＲ－Ｎ」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）＋東ソー株式会社製「ＴＳＫ－ＧＥＬ　ＧＭＨＨＲ－Ｎ」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）＋東ソー株式会社製「ＴＳＫ－ＧＥＬ　ＧＭＨＨＲ－Ｎ」（７．８ｍｍＩ．Ｄ．×３０ｃｍ）
　検出器：ＥＬＳＤ（オルテック製「ＥＬＳＤ２０００」）
　データ処理：東ソー株式会社製「ＧＰＣ－８０２０モデルＩＩデータ解析バージョン４．３０」
　測定条件：カラム温度　　４０℃
　　　　　　展開溶媒　　　テトラヒドロフラン（ＴＨＦ）
　　　　　　流速　　　　　１．０ｍｌ／分
　試料：樹脂固形分換算で１．０質量％のテトラヒドロフラン溶液をマイクロフィルターでろ過したもの（５μｌ）。
　標準試料：前記「ＧＰＣ－８０２０モデルＩＩデータ解析バージョン４．３０」の測定マニュアルに準拠して、分子量が既知の下記の単分散ポリスチレンを用いた。 [GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HHR-H” (6.0 mm ID × 4 cm) manufactured by Tosoh Corporation + “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) manufactured by Tosoh Corporation + Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation “TSK-GEL GMHHR-N” (7.8 mm ID × 30 cm) + Tosoh Corporation “TSK- GEL GMHHR-N "(7.8 mm ID x 30 cm)
Detector: ELSD ("ELSD2000" manufactured by Oltec)
Data processing: “GPC-8020 Model II data analysis version 4.30” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran (THF)
Flow rate: 1.0 ml / min Sample: A 1.0% by mass tetrahydrofuran solution in terms of resin solid content filtered through a microfilter (5 μl).
Standard sample: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II Data Analysis Version 4.30”.
　（単分散ポリスチレン）
　東ソー株式会社製「Ａ－５００」
　東ソー株式会社製「Ａ－１０００」
　東ソー株式会社製「Ａ－２５００」
　東ソー株式会社製「Ａ－５０００」
　東ソー株式会社製「Ｆ－１」
　東ソー株式会社製「Ｆ－２」
　東ソー株式会社製「Ｆ－４」
　東ソー株式会社製「Ｆ－１０」
　東ソー株式会社製「Ｆ－２０」
　東ソー株式会社製「Ｆ－４０」
　東ソー株式会社製「Ｆ－８０」
　東ソー株式会社製「Ｆ－１２８」
　東ソー株式会社製「Ｆ－２８８」
　東ソー株式会社製「Ｆ－５５０」 (Monodispersed polystyrene)
“A-500” manufactured by Tosoh Corporation
“A-1000” manufactured by Tosoh Corporation
“A-2500” manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
“F-2” manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
“F-288” manufactured by Tosoh Corporation
“F-550” manufactured by Tosoh Corporation
　本発明で用いる重合体（Ｘ）を製造する方法としては、例えば、キャスト重合、塊状重合、懸濁重合、溶液重合、乳化重合、アニオン重合等の種々の重合方法を用いることができる。製造方法の中でも、塊状重合や溶液重合が、微小な異物の混入が少ない重合体が得られることから好ましい。溶液重合を行う場合には、原料の混合物をトルエン、エチルベンゼン等の芳香族炭化水素の溶媒に溶解して調整した溶液を用いることができる。塊状重合により重合させる場合には、通常行われるように加熱により生じる遊離ラジカルや電離性放射線照射により重合を開始させることができる。 As the method for producing the polymer (X) used in the present invention, for example, various polymerization methods such as cast polymerization, bulk polymerization, suspension polymerization, solution polymerization, emulsion polymerization, anionic polymerization and the like can be used. Among the production methods, bulk polymerization and solution polymerization are preferable because a polymer with a small amount of minute foreign matters can be obtained. When solution polymerization is performed, a solution prepared by dissolving a mixture of raw materials in an aromatic hydrocarbon solvent such as toluene or ethylbenzene can be used. In the case of polymerization by bulk polymerization, the polymerization can be started by irradiation with free radicals generated by heating or ionizing radiation as is usually done.
　前記重合反応に用いられる開始剤としては、一般にラジカル重合において用いられる任意の開始剤を使用することができ、例えば、アゾビスイソブチルニトリル等のアゾ化合物；ベンゾイルパーオキサイド、ラウロイルパーオキサイド、ｔ－ブチルパーオキシ－２－エチルヘキサノエート等の有機過酸化物等が用いられる。重合する際に、９０℃以上の高温下で重合を行わせる場合には、溶液重合が一般的であるので、１０時間半減期温度が８０℃以上でかつ用いる有機溶媒に可溶である過酸化物、アゾビス開始剤などが好ましく、具体的には１，１－ビス（ｔ－ブチルパーオキシ）３，３，５－トリメチルシクロヘキサン、シクロヘキサンパーオキシド、２，５－ジメチル－２，５－ジ（ベンゾイルパーオキシ）ヘキサン、１，１－アゾビス（１－シクロヘキサンカルボニトリル）、２－（カルバモイルアゾ）イソブチロニトリル等を挙げることができる。これらの開始剤は０．００５～５質量％の範囲で用いられる。 As the initiator used in the polymerization reaction, any initiator generally used in radical polymerization can be used. For example, azo compounds such as azobisisobutylnitrile; benzoyl peroxide, lauroyl peroxide, t-butyl An organic peroxide such as peroxy-2-ethylhexanoate is used. When the polymerization is carried out at a high temperature of 90 ° C. or higher, solution polymerization is generally used, so that the 10-hour half-life temperature is 80 ° C. or higher and the peroxide is soluble in the organic solvent used. And azobis initiators are preferred. Specifically, 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, cyclohexane peroxide, 2,5-dimethyl-2,5-di ( Benzoylperoxy) hexane, 1,1-azobis (1-cyclohexanecarbonitrile), 2- (carbamoylazo) isobutyronitrile and the like can be mentioned. These initiators are used in the range of 0.005 to 5% by mass.
　本発明で用いる重合体（Ｘ）を重合する際には、必要に応じて分子量調整剤を使用しても良い。前記分子量調節剤は、一般的なラジカル重合において用いる任意のものが使用され、例えば、ブチルメルカプタン、オクチルメルカプタン、ドデシルメルカプタン、チオグリコール酸２－エチルヘキシル等のメルカプタン化合物が特に好ましいものとして挙げられる。これらの分子量調節剤は、重合度が上記の範囲内に制御されるような濃度範囲で添加される。 When polymerizing the polymer (X) used in the present invention, a molecular weight modifier may be used as necessary. As the molecular weight regulator, any one used in general radical polymerization is used, and for example, mercaptan compounds such as butyl mercaptan, octyl mercaptan, dodecyl mercaptan, 2-ethylhexyl thioglycolate are particularly preferable. These molecular weight regulators are added in a concentration range such that the degree of polymerization is controlled within the above range.
　本発明で用いるエステル化合物（Ｙ）は、下記一般式（１）
Ｂ－（Ｇ－Ａ）ｎ－Ｇ－Ｂ　　　　（１）
　（式中、Ｂは炭素原子数６～１２の芳香族モノカルボン酸の残基であり、Ｇは炭素原子数２～１２のアルキレングリコールの残基または炭素原子数４～１２のオキシアルキレングリコールの残基であり、Ａはジカルボン酸の残基であり、ｎは繰り返し数であって０～３０の整数であり、繰り返しごとにＧ及びＡは同一でも異なっていてもよく、式中に複数あるＢ及びＧは同一でも異なっていても良い。）
で表され、末端が芳香族カルボン酸の残基で封止されていることを特徴とする。末端を芳香族モノカルボン酸の残基で封止することにより前記重合体（Ｘ）との相溶性、すなわち透明性に優れ、転写紙として好適なフィルム層を形成することができる。 The ester compound (Y) used in the present invention has the following general formula (1):
B- (GA) n -GB (1)
Wherein B is a residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms, and G is a residue of an alkylene glycol having 2 to 12 carbon atoms or an oxyalkylene glycol having 4 to 12 carbon atoms. A residue, A is a residue of a dicarboxylic acid, n is the number of repetitions and is an integer of 0 to 30, and G and A may be the same or different for each repetition, and there are a plurality of them in the formula B and G may be the same or different.)
And the terminal is sealed with an aromatic carboxylic acid residue. By sealing the terminal with a residue of an aromatic monocarboxylic acid, a film layer excellent in compatibility with the polymer (X), that is, excellent in transparency and suitable as a transfer paper can be formed.
　本発明で用いるエステル化合物（Ｙ）は、重合体（Ｘ）との相溶性、及び可塑化効果、成形加工時のブリード抑制、フィルムとした際の強度と柔軟性とのバランスの観点より、数平均分子量（Ｍｎ）が２００～３０００の範囲であることが好ましく、特に２５０～１５００の範囲であることが好ましい。これらの点から、繰り返し数を示すｎとしては、０～３０の整数であるが、その平均値としては、０～５の範囲であることが好ましい。 The ester compound (Y) used in the present invention is several from the viewpoint of compatibility with the polymer (X), plasticizing effect, bleed suppression during molding, and balance between strength and flexibility when used as a film. The average molecular weight (Mn) is preferably in the range of 200 to 3000, and particularly preferably in the range of 250 to 1500. From these points, n indicating the number of repetitions is an integer of 0 to 30, but the average value is preferably in the range of 0 to 5.
　前記一般式（１）中のＢは前記の通り炭素原子数６～１２の芳香族モノカルボン酸の残基である。尚、ここでの炭素原子数は、カルボキシ基中の炭素原子を含まない。芳香族モノカルボン酸の残基における「残基」とは、カルボキシ基中の末端の水素原子を含まない物を言う。 B in the general formula (1) is a residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms as described above. The number of carbon atoms here does not include carbon atoms in the carboxy group. The “residue” in the residue of an aromatic monocarboxylic acid refers to a substance that does not contain a terminal hydrogen atom in a carboxy group.
　前記芳香族モノカルボン酸としては、例えば、安息香酸、ジメチル安息香酸、トリメチル安息香酸、テトラメチル安息香酸、エチル安息香酸、プロピル安息香酸、ブチル安息香酸、クミン酸、パラターシャリブチル安息香酸、オルソトルイル酸、メタトルイル酸、パラトルイル酸、エトキシ安息香酸、プロポキシ安息香酸、ナフトエ酸、ニコチン酸、フロ酸、アニス酸等が挙げられ、これらの中でも、後述する製法にて容易に本発明のエステル化合物（Ｙ）を合成できる観点、工業的原料入手容易性の観点、及び得られる樹脂組成物の成型加工性や積層体（転写紙）とした際の引張特性により優れる点より、安息香酸であることが好ましい。 Examples of the aromatic monocarboxylic acid include benzoic acid, dimethyl benzoic acid, trimethyl benzoic acid, tetramethyl benzoic acid, ethyl benzoic acid, propyl benzoic acid, butyl benzoic acid, cumic acid, para-tert-butyl benzoic acid, orthotoluyl. Acid, metatoluic acid, p-toluic acid, ethoxybenzoic acid, propoxybenzoic acid, naphthoic acid, nicotinic acid, furoic acid, anisic acid and the like. Among these, the ester compound (Y ) From the viewpoint of being able to synthesize, the availability of industrial raw materials, and the molding processability of the resulting resin composition and the tensile properties when made into a laminate (transfer paper), benzoic acid is preferred. .
　前記一般式（１）中のＧは、前記の通り、炭素原子数２～１２のアルキレングリコールの残基または炭素原子数４～１２のオキシアルキレングリコールの残基である。ここでの残基とは、グルコールにおける水酸基を除いた基のことを言う。 G in the general formula (1) is, as described above, 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 residue here means the group except the hydroxyl group in glycol.
　前記炭素原子数２～１２のアルキレングリコールとしては、例えば、エチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、２－メチル－１，３－プロパンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、２，２－ジメチル－１，３－プロパンジオール（ネオペンチルグリコール）、２，２－ジエチル－１，３－プロパンジオール（３，３－ジメチロ－ルペンタン）、２－ｎ－ブチル－２－エチル－１，３プロパンジオール（３，３－ジメチロールヘプタン）、３－メチル－１，５－ペンタンジオール、１，６－ヘキサンジオール、２，２，４－トリメチル１，３－ペンタンジオール、２－エチル－１，３－ヘキサンジオール、２－メチル－１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、１，１２－ドデカンジオール等が挙げられる。これらの中でも、重合体（Ｘ）との相溶性に優れる観点から、エチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、２－メチル－１，３－プロパンジオールが好ましく、エチレングリコール、１，２－プロピレングリコールがより好ましい。 Examples of the alkylene glycol having 2 to 12 carbon atoms include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl- 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propane Diol (3,3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentanediol, 1,6 -Hexanediol, 2,2,4-trimethyl 1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl Le-1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, and the like. Among these, from the viewpoint of excellent compatibility with the polymer (X), ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, -Methyl-1,3-propanediol is preferred, and ethylene glycol and 1,2-propylene glycol are more preferred.
　また、炭素原子数４～１２のオキシアルキレングリコールとしては、例えば、ジエチレングリコール、トリエチレングリコール、テトラエチレングリコール、ジプロピレングリコール、トリプロピレングリコール等が挙げられる。 Examples of the oxyalkylene glycol having 4 to 12 carbon atoms include diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol, and tripropylene glycol.
　前記一般式（１）中のＡは、ジカルボン酸の残基であり、脂肪族化合物、芳香族化合物のいずれのジカルボン酸の残基であっても良い。ここでの残基の意味は、前記と同じである。 A in the general formula (1) is a residue of a dicarboxylic acid, and may be a residue of a dicarboxylic acid of either an aliphatic compound or an aromatic compound. The meaning of the residue here is the same as described above.
　前記ジカルボン酸としては、炭素原子数２～１２のアルキレンジカルボン酸であることが、本発明の効果をより発現しやすい観点から好ましく、例えば、シュウ酸、マロン酸、コハク酸、グルタル酸、アジピン酸、マレイン酸、フマル酸、１，２－ジカルボキシシクロヘキサン、１，２－ジカルボキシシクロヘキセン等が挙げられる。これらの中でも、より引張特性等に優れるフィルム層が得られやすい観点からコハク酸、アジピン酸、１，２－ジカルボキシシクロヘキサンであることが好ましく、アジピン酸であることが特に好ましい。 The dicarboxylic acid is preferably an alkylene dicarboxylic acid having 2 to 12 carbon atoms from the viewpoint of more easily expressing the effects of the present invention. For example, 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 easily obtaining a film layer having more excellent tensile properties.
　更に芳香族ジカルボン酸としては、例えば、フタル酸、テレフタル酸、イソフタル酸、１，４－ナフタレンジカルボン酸、２，３－ナフタレンジカルボン酸、２，６－ナフタレンジカルボン酸、２，７－ナフタレンジカルボン酸、１，８－ナフタレンジカルボン酸等が挙げられる。これらの中でも、より強度が高いフィルム層が得られやすい点から、フタル酸、テレフタル酸、イソフタル酸であることが好ましく、フタル酸が最も好ましい。 Further, 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, and 2,7-naphthalenedicarboxylic acid. 1,8-naphthalenedicarboxylic acid and the like. Among these, phthalic acid, terephthalic acid, and isophthalic acid are preferable, and phthalic acid is most preferable because a film layer with higher strength can be easily obtained.
　前記一般式（１）で表されるエステル化合物（Ｙ）は、例えば、下記に示す方法で得ることができる。
　方法１：一般式（１）の各残基を構成する芳香族モノカルボン酸又は芳香族モノカルボン酸誘導体、ジカルボン酸及びグリコールを一括で仕込み、これらを反応させる方法。
　方法２：一般式（１）の残基を構成するジカルボン酸とグリコールとを、水酸基の当量がカルボキシル基の当量よりも多くなる条件下で反応させて水酸基を主鎖の末端に有する化合物を得た後、該化合物と芳香族モノカルボン酸または芳香族モノカルボン酸誘導体とを反応させる方法。 The ester compound (Y) represented by the general formula (1) can be obtained, for example, by the method shown below.
Method 1: A method in which an aromatic monocarboxylic acid or an aromatic monocarboxylic acid derivative, a dicarboxylic acid and a glycol constituting each residue of the general formula (1) are charged together and reacted.
Method 2: A compound having a hydroxyl group at the end of the main chain is obtained by reacting the dicarboxylic acid constituting the residue of the general formula (1) with glycol under the condition that the equivalent of the hydroxyl group is larger than the equivalent of the carboxyl group. And then reacting the compound with an aromatic monocarboxylic acid or an aromatic monocarboxylic acid derivative.
　前記の方法１、２における芳香族モノカルボン酸、ジカルボン酸及びグリコールは、前述の残基についてのべている原料と同様であり、単独の化合物のみを用いても、２種以上を併用しても良い。芳香族モノカルボン酸誘導体は、前記の芳香族モノカルボン酸を用いた場合と同様にグルコールと反応してエステル結合を形成しうるものであればよく、例えば、そのエステル化物、酸塩化物等が挙げられる。 The aromatic monocarboxylic acid, dicarboxylic acid and glycol in the above methods 1 and 2 are the same as the raw materials mentioned for the above-mentioned residues, and even if only a single compound is used, two or more kinds are used in combination. Also good. The aromatic monocarboxylic acid derivative is not particularly limited as long as it can react with glycol to form an ester bond in the same manner as in the case of using the aromatic monocarboxylic acid, and examples thereof include esterified products, acid chlorides, and the like. Can be mentioned.
　方法１、２のいずれにおいても、前記の原料を、必要に応じてエステル化触媒の存在下で、例えば、１８０～２５０℃の温度範囲内で１０～２５時間、エステル化反応させることにより製造することができる。尚、エステル化反応の温度、時間などの条件は特に限定せず、適宜設定してよい。 In both methods 1 and 2, the raw material is produced by an esterification reaction in the presence of an esterification catalyst as necessary, for example, within a temperature range of 180 to 250 ° C. for 10 to 25 hours. be able to. In addition, conditions, such as temperature of esterification reaction and time, are not specifically limited, You may set suitably.
　前記エステル化触媒としては、例えば、テトライソプロピルチタネート、テトラブチルチタネート等のチタン系触媒；ジブチル錫オキサイド等のスズ系触媒；ｐ－トルエンスルホン酸等の有機スルホン酸系触媒などが挙げられる。 Examples of the esterification catalyst include titanium catalysts such as tetraisopropyl titanate and tetrabutyl titanate; tin catalysts such as dibutyltin oxide; and organic sulfonic acid catalysts such as p-toluenesulfonic acid.
　前記エステル化触媒の使用量は、適宜設定すればよいが、通常、原料の全量１００質量部に対して、０．００１～０．１質量部の範囲で使用することが好ましい。 The amount of the esterification catalyst used may be set as appropriate, but usually it is preferably used in the range of 0.001 to 0.1 parts by mass with respect to 100 parts by mass of the total amount of raw materials.
　本発明でのエステル化合物（Ｙ）の性状は、その数平均分子量や原料の組み合わせなどの要因により異なるが、通常、常温にて液体、固体、ペースト状などである。 The properties of the ester compound (Y) in the present invention vary depending on factors such as the number average molecular weight and the combination of raw materials, but are usually liquid, solid, paste, etc. at room temperature.
　本発明でのエステル化合物（Ｙ）の酸価としては、重合体（Ｘ）と相溶性がより良好である観点から５以下が好ましく、１以下がより好ましい。また、同様の理由により水酸基価は５０以下が好ましく、２０以下がより好ましい。 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, more preferably 20 or less.
　本発明の転写紙用樹脂組成物中のエステル化合物（Ｙ）の含有量は、使用する重合体（Ｘ）の分子量やそのガラス転移温度等にもよるが、樹脂組成物としての成型性が良好であり、得られるフィルム層の引張特性等とのバランスもとりやすい点から前記重合体（Ｘ）１００質量部に対して３～５０質量部が好ましく、５～３０質量部がより好ましく、１０～２０質量部が更に好ましい。 Although 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 and its glass transition temperature, the moldability as a resin composition is good. From the viewpoint that it is easy to balance with the tensile properties and the like of the obtained film layer, it is preferably 3 to 50 parts by weight, more preferably 5 to 30 parts by weight with respect to 100 parts by weight of the polymer (X). Part by mass is more preferable.
　本発明の転写紙用樹脂組成物は、絵付け用転写紙の作製に好ましく用いられ、印刷インキ層上に印刷等によって塗布されるが、塗布に際しては本発明の転写紙用樹脂組成物を各種有機溶剤によって希釈して粘度５００～５０００ｍＰａ・ｓ、固形分２０～６０質量％の溶液状とすることが好ましく、特に５００～３０００ｍＰａ・ｓ、３０～５０質量％がより好ましい。樹脂組成物の粘度は、Ｂ型粘度計を用い、２５℃、回転数６０ｒｐｍで測定される値である。 The resin composition for transfer paper of the present invention is preferably used for the production of a transfer paper for painting, and is applied on the printing ink layer by printing or the like. It is preferably diluted with an organic solvent to form a solution having a viscosity of 500 to 5000 mPa · s and a solid content of 20 to 60% by mass, and more preferably 500 to 3000 mPa · s and 30 to 50% by mass. The viscosity of the resin composition is a value measured using a B-type viscometer at 25 ° C. and a rotation speed of 60 rpm.
　溶剤としては、たとえば、トルエン、キシレン、エチルベンゼン等の芳香族系溶剤；酢酸エチル、酢酸ノルマルブチル、酢酸イソブチル、酢酸ノルマルプロピル、酢酸イソプロピル、酢酸アミル等の酢酸エステル系溶剤；メチルイソブチルケトン、メチルエチルケトン、ジイソブチルケトン、アセトン等のケトン系溶剤；メタノール、エタノール、イソプロピルアルコール、ノルマルプロピルアルコール、ノルマルブチルアルコール、イソブチルアルコール、ターシャリブチルアルコール、ベンジルアルコール等のアルコール系溶剤；エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール等のグリコール系溶剤；エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル等のグリコールエーテル系溶剤；メチルセロソルブアセテート、メトキシプロピルアセテート等のアセテート系溶剤；ノルマルヘキサン、シクロへキサン、メチルシクロへキサン、ヘプタン等の炭化水素系溶剤；エクソンモービル株式会社のソルベッソ１００、ソルベッソ１５０、ソルベッソ２００、丸善石油株式会社のスワゾール（登録商標）１０００、スワゾール１５００、スワゾール１８００、出光興産株式会社のイプゾール（登録商標）１００、イプゾール１５０等のナフサ系溶剤；エクソンモービル株式会社のエクソールＤ３０、エクソールＤ４０等のナフテン系溶剤；エクソンモービル株式会社のアイソパー（登録商標）Ｅ、アイソパーＧ、アイソパーＨ、アイソパーＬ、アイソパーＭ等のイソパラフィン系溶剤；等が挙げられ、単独でも2種以上を混合して使用しても良い。 Examples of the solvent include aromatic solvents such as toluene, xylene and ethylbenzene; acetate solvents such as ethyl acetate, normal butyl acetate, isobutyl acetate, normal propyl acetate, isopropyl acetate and amyl acetate; methyl isobutyl ketone, methyl ethyl ketone, Ketone solvents such as diisobutyl ketone and acetone; alcohol solvents such as methanol, ethanol, isopropyl alcohol, normal propyl alcohol, normal butyl alcohol, isobutyl alcohol, tertiary butyl alcohol, and benzyl alcohol; ethylene glycol, diethylene glycol, triethylene glycol, Glycol solvents such as propylene glycol; ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, etc. Glycol ether solvents; acetate solvents such as methyl cellosolve acetate and methoxypropyl acetate; hydrocarbon solvents such as normal hexane, cyclohexane, methylcyclohexane and heptane; Solvesso 100, Solvesso 150, Solvesso 200 from ExxonMobil Corporation , Naphtha solvents such as SWAZOL (registered trademark) 1000, SWAZOL 1500, SWAZOL 1800, IZUMO Kosan Co., Ltd., Ipsol 150, IPZOL 150, etc .; Naphthenic solvents; Isopar (registered trademark) E, Isopar G, Isopar H, Isopar L, Isopar M and other isoparaffinic solvents from ExxonMobil Corporation; It may be used in a mixture of two or more of them in Germany.
　溶剤は、重合体（Ｘ）、エステル化合物（Ｙ）及び必要により併用されるその他の成分を配合する際に、これらの成分とともに配合される溶媒も包含する。このような溶媒としては、例えば、後述のポリシロキサン等を溶解するのに使用されるシクロヘキサノン及びイソブチルケトン、可塑剤を溶解するのに使用されるミネラルスピリット等が挙げられる。これらの溶剤はいずれか１種を単独で、または複数種を組み合わせて用いることができる。 The solvent includes a solvent blended with these components when blending the polymer (X), the ester compound (Y), and other components used in combination as necessary. Examples of such a solvent include cyclohexanone and isobutyl ketone used for dissolving polysiloxane described later, mineral spirit used for dissolving a plasticizer, and the like. Any one of these solvents may be used alone or in combination of two or more.
　これらの中でも、印刷等により樹脂組成物を塗布した際の飛び散り、糸曳きをなくす観点、また重合体（Ｘ）の溶解性の観点から、ナフサ系溶剤が好ましく、ソルベッソ１００、ソルベッソ１５０、ソルベッソ２００、スワゾール１０００、スワゾール１５００、スワゾール１８００がより好ましく、ソルベッソ１００、スワゾール１０００がさらに好ましい。樹脂組成物が通常スクリーン印刷、平板印刷等により印刷塗布されるので、蒸発速度、溶解力、臭気等を考慮し、比較的高沸点のものが好ましく、ナフテン系溶剤、ソルベントナフサ系溶剤、セロソロブ系溶剤等が好ましく用いられる。 Among these, a naphtha solvent is preferable from the viewpoint of eliminating scattering and stringing when the resin composition is applied by printing or the like, and from the viewpoint of solubility of the polymer (X), and Solvesso 100, Solvesso 150, Solvesso 200. , Swazol 1000, Swazol 1500, and Swazole 1800 are more preferable, and Solvesso 100 and Swazol 1000 are more preferable. Since the resin composition is usually printed and applied by screen printing, flat printing, etc., in consideration of evaporation rate, dissolving power, odor, etc., those having a relatively high boiling point are preferred. Naphthenic solvents, solvent naphtha solvents, cellosolve solvents A solvent or the like is preferably used.
　本発明の樹脂組成物は、前述したような従来広く採用されている転写紙の作製方法、転写紙を用いての絵付け方法に好ましく適用され、良好な剥離性を有し、印刷インキの経時での滲みを防止し、かつフィルム物性、耐ブロッキング性、印刷適性に優れるものである。 The resin composition of the present invention is preferably applied to a transfer paper preparation method widely used in the past as described above and a painting method using the transfer paper, and has a good releasability, and the aging of the printing ink. The film has excellent physical properties, anti-blocking properties and printability.
　本発明の転写紙用樹脂組成物には、その他印刷等での塗布時の粘度安定性、柔軟性、消泡性、乾燥性等を満足させるために、本発明でのエステル化合物（Ｙ）以外の可塑剤、揺変剤、消泡剤等の助剤を添加することができる。これら添加される助剤はその合計量で重合体（Ｘ）１００質量部に対し、１５質量部を超えない量、好ましくは１０質量部を超えない量添加することにより印刷適性、貼り適性がより良好となる。 In addition to the ester compound (Y) of the present invention, the resin composition for transfer paper of the present invention satisfies the viscosity stability, flexibility, antifoaming property, drying property, etc. at the time of application in other printing. Auxiliaries such as plasticizers, thixotropic agents and antifoaming agents can be added. These added auxiliaries are added in an amount not exceeding 15 parts by mass, and preferably not exceeding 10 parts by mass, with respect to 100 parts by mass of the polymer (X) in terms of the total amount. It becomes good.
　本発明の転写紙用樹脂組成物から形成されるフィルム層を剥離して除去する絵付け方法を用いる場合には、本発明の転写紙用樹脂組成物に更にシリカを混合することで、印刷等により樹脂組成物を塗布し、フィルム層を形成する際に消泡性を発現させ、成膜性を高めることができる。シリカは粉末シリカであることが好ましく、たとえば煙霧質シリカ、沈降シリカ、焼成シリカ等が挙げられる。これらはいずれか１種を単独で、または複数種を組み合わせて用いることができる。更に、表面未処理シリカであってもよく、表面が疎水化処理されたシリカであってもよい。表面未処理シリカの表面は通常、親水性である。疎水化処理することで、分散性、湿潤性、流動性を向上できる。 When using a painting method in which the film layer formed from the resin composition for transfer paper of the present invention is peeled and removed, printing is performed by further mixing silica with the resin composition for transfer paper of the present invention. When the resin composition is applied to form a film layer, the defoaming property can be expressed and the film forming property can be improved. The silica is preferably powdered silica, and examples thereof include fumed silica, precipitated silica, and fired silica. Any of these may be used alone or in combination of two or more. Furthermore, the surface untreated silica may be sufficient and the silica by which the surface was hydrophobized may be sufficient. The surface of the untreated silica is usually hydrophilic. By performing the hydrophobizing treatment, dispersibility, wettability, and fluidity can be improved.
　シリカ表面の疎水化処理は、種々の方法によって行うことができ、たとえばオルガノクロロシラン、オルガノアルコキシシラン、オルガノジシラザン、オルガノポリシロキサン、オルガノハイドロジェンポリシロキサン等の有機ケイ素化合物でシリカ表面を処理する方法が挙げられる。 Hydrophobic treatment of the silica surface can be performed by various methods, for example, a method of treating the silica surface with an organosilicon compound such as organochlorosilane, organoalkoxysilane, organodisilazane, organopolysiloxane, organohydrogenpolysiloxane, etc. Is mentioned.
　前記シリカの比表面積（ＢＥＴ法）は５０ｍ２／ｇ以上であることが好ましく、１００～７００ｍ２／ｇがより好ましく、１５０～５００ｍ２／ｇがさらに好ましい。比表面積は大きいほど消泡性能が向上し、成膜性が向上する。シリカの含有量としては、消泡性と成膜性により優れ、また、樹脂組成物の粘度が適正な範囲で、作業性が良好である点より、重合体（Ｘ）１００質量部に対して０．００１～１０質量部が好ましく、０．０１～５質量部がより好ましい。 The specific surface area (BET method) of the silica is preferably 50 m 2 / g or more, more preferably 100 to 700 m 2 / g, and even more preferably 150 to 500 m 2 / g. The larger the specific surface area, the better the defoaming performance and the better the film formability. As content of silica, it is excellent in defoaming property and film-forming property, and the viscosity of the resin composition is in an appropriate range, and the workability is good, so that the polymer (X) is 100 parts by mass. 0.001 to 10 parts by mass is preferable, and 0.01 to 5 parts by mass is more preferable.
　本発明の転写紙用樹脂組成物から形成されるフィルム層を剥離して除去する絵付け方法を用いる場合には、本発明の転写紙用樹脂組成物に更にポリシロキサンを併用することで、インキ層からの良好な剥離性を発現させることができる。ポリシロキサンとしては、たとえばポリエーテル変性ポリジメチルシロキサン、ポリエステル変性ポリジメチルシロキサン、ポリエーテル変性ポリメチルアルキルシロキサン、アラルキル変性ポリメチルアルキルシロキサン、ポリエーテル変性シロキサン、ポリエステル変性水酸基含有ポリジメチルシロキサン等が挙げられる。これらはいずれか１種を単独で、または複数種を組み合わせて用いることができる。これらの中でも種々インキ層からの剥離性や成膜性の観点から、ポリエーテル変性ポリジメチルシロキサン、アラルキル変性ポリメチルアルキルシロキサン、ポリエーテル変性シロキサンを用いることが好ましい。 In the case of using a painting method in which the film layer formed from the resin composition for transfer paper of the present invention is peeled and removed, by further using polysiloxane in combination with the resin composition for transfer paper of the present invention, an ink is obtained. Good peelability from the layer can be developed. Examples of the polysiloxane include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyether-modified polymethylalkylsiloxane, aralkyl-modified polymethylalkylsiloxane, polyether-modified siloxane, and polyester-modified hydroxyl group-containing polydimethylsiloxane. . Any of these may be used alone or in combination of two or more. Of these, polyether-modified polydimethylsiloxane, aralkyl-modified polymethylalkylsiloxane, and polyether-modified siloxane are preferably used from the viewpoints of peelability from various ink layers and film formability.
　前記ポリシロキサンとしては、剥離性と成膜性のバランスがより良好である観点より、重量平均分子量が５０～２３０のポリシロキサンと、重量平均分子量が３８０～１５００のポリシロキサンとから構成されることが好ましい。ポリシロキサンの含有量としては、剥離性と成膜性のバランスがより良好である点から、重合体（Ｘ）１００質量部に対して０．０１～１０質量部が好ましく、０．０１～５質量部がより好ましい。 The polysiloxane is 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 a better balance between peelability and film formability. Is preferred. The content of the polysiloxane is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the polymer (X) from the viewpoint of a better balance between peelability and film formability, and 0.01 to 5 parts. Part by mass is more preferable.
　本発明でのエステル化合物（Ｙ）は重合体（Ｘ）の可塑剤としての機能を有するものであるが、従来可塑剤として使用されているものを、本発明の効果を損なわない範囲で適宜併用しても良い。その他の可塑剤としては例えば、リン酸トリクレシル等のリン酸トリアリール系、リン酸トリアルキル系、リン酸アルキルアリール系等のリン酸エステル；アジピン酸ジブチル、アジピン酸ジオクチル等の脂肪族二塩基酸エステル；ポリエチレングリコール、ポリプロピレングリコール、ジブチルグリコールアジペート等のエーテル結合含有化合物；ポリエステル系化合物；エポキシ化大豆油等の大豆油系化合物；等が挙げられる。これらの可塑剤はいずれか１種を単独で、または複数種を組み合わせて用いることができる。 The ester compound (Y) in the present invention has a function as a plasticizer of the polymer (X), but those conventionally used as a plasticizer are appropriately used in a range not impairing the effects of the present invention. You may do it. Examples of other plasticizers include phosphate esters such as triaryl phosphates such as tricresyl phosphate, trialkyl phosphates and alkylaryl phosphates; aliphatic dibasic acids such as dibutyl adipate and dioctyl adipate Examples include esters; compounds containing ether bonds such as polyethylene glycol, polypropylene glycol, dibutyl glycol adipate; polyester compounds; soybean oil compounds such as epoxidized soybean oil; These plasticizers can be used alone or in combination of two or more.
　本発明の樹脂組成物に混合されるその他の添加剤としては、たとえば、印刷等での塗布時の粘度安定性、柔軟性、乾燥性等を満足させるために、チキソ剤等の助剤を含むことができる。チキソ剤としては、たとえば脂肪酸アマイド系ワックス、アミド系ワックス、ヒマシ油、水添ヒマシ油等が挙げられる。 As other additives mixed in the resin composition of the present invention, for example, an auxiliary agent such as a thixotropic agent is included in order to satisfy viscosity stability, flexibility, drying property, etc. at the time of application in printing or the like. be able to. Examples of the thixotropic agent include fatty acid amide wax, amide wax, castor oil, hydrogenated castor oil, and the like.
　本発明の樹脂組成物の製造方法としては、特に限定されるものではなく、撹拌機、冷却管、温度計を備えた撹拌装置に溶剤を仕込み、これを撹拌しながら重合体（Ｘ）を少しずつ添加し、重合体（Ｘ）が溶解したのを確認した後、エステル化合物（Ｙ）、及びその他併用される各種添加剤などを、添加する方法が好ましい。 The method for producing the resin composition of the present invention is not particularly limited. A solvent is charged into a stirrer equipped with a stirrer, a cooling tube, and a thermometer, and the polymer (X) is slightly added while stirring this. A method of adding the ester compound (Y) and other various additives that are used in combination after adding the polymer (X) and confirming that the polymer (X) is dissolved is preferable.
　本発明の樹脂組成物は、転写紙に用いられる。たとえば、台紙と水溶性糊剤層とインキ層とフィルム層とがこの順に積層した積層体からなる転写紙の前記フィルム層を形成するために本発明の樹脂組成物が用いられる。 The resin composition of the present invention is used for transfer paper. For example, the resin composition of the present invention is used to form the film layer of transfer paper comprising a laminate in which a backing paper, a water-soluble paste layer, an ink layer, and a film layer are laminated in this order.
　本発明の積層体は、前記の様に、例えば、台紙と、水溶性糊剤層と、インキ層と、フィルム層とがこの順に積層したものである。水溶性糊剤層は、台紙の全面を覆うように形成されている。インキ層は、水溶性糊剤層上に部分的に形成されている。フィルム層は、インキ層を被覆するように形成されている。フィルム層の一部は水溶性糊剤層と接していても良い As described above, the laminate of the present invention is a laminate in which, for example, a mount, 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 mount. The ink layer is partially formed on the water-soluble paste layer. The film layer is formed so as to cover the ink layer. Part of the film layer may be in contact with the water-soluble paste layer
　台紙としては、吸水性のよい台紙（和紙）等が挙げられる。水溶性糊剤層を形成する水溶性糊剤としては、澱粉、ポリビニルアルコール、カルボキシメチルセルロース等が挙げられる。インキ層としては、熱硬化型インキ、熱可塑性インキ、ＵＶ硬化型インキ等が挙げられる。インキ層は、積層体を絵付け用転写紙として用いる場合には、陶磁器等に転写される絵柄で形成される。インキ層は、単層でもよく多層でもよい。 Examples of the mount include a mount (Japanese paper) having good water absorption. Examples of the water-soluble paste forming the water-soluble paste layer include starch, polyvinyl alcohol, carboxymethyl cellulose and the like. Examples of the ink layer include thermosetting ink, thermoplastic ink, and UV curable ink. When the laminate is used as a transfer sheet for painting, the ink layer is formed with a pattern transferred to a ceramic or the like. The ink layer may be a single layer or a multilayer.
　フィルム層は、前述の本発明の樹脂組成物の乾燥物からなるものであり、重合体（Ｘ）と、エステル化合物（Ｙ）、及びその他併用される、ポリシロキサン、シリカ、可塑剤等のその他添加剤が含まれる。乾燥は、溶剤を揮発できればよい。 The film layer is composed of a dried product of the above-described resin composition of the present invention. The polymer (X), the ester compound (Y), and other used in combination, such as polysiloxane, silica, and plasticizer Additives are included. The drying is not limited as long as the solvent can be volatilized.
　積層体は、たとえば、水溶性糊剤が塗布されて水溶性糊剤層が形成された台紙の上に、インキを用いてインキ層を形成し、その上に本発明の樹脂組成物を塗布し、乾燥してフィルム層を形成することで製造できる。 The laminate is formed, for example, by forming an ink layer using ink on a mount on which a water-soluble paste layer is applied to form a water-soluble paste layer, and the resin composition of the present invention is applied thereon. It can be produced by drying to form a film layer.
　積層体を絵付け用転写紙として用いる場合、たとえば、以下のようにして絵付けを行うことができる。まず、積層体を水または温水に浸漬し、水溶性糊剤層を溶解させて、インキ層の付いたフィルム層を台紙から剥離する。このインキ層の付いたフィルム層を、陶磁器等の所定の位置に、陶磁器等とインキ層とが接触するように配置する。そして、インキ層の付いたフィルム層と陶磁器等との間の水分、気泡等を除去した後、フィルム層のみを剥離もしくは焼成する。これにより、陶磁器等の表面にインキ層が残り、絵付けが行われる。 When the laminate is used as a transfer paper for painting, for example, painting can be performed 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 mount. The film layer with the ink layer is disposed at a predetermined position of the ceramic or the like so that the ceramic or the like and the ink layer are in contact with each other. And after removing the water | moisture content, air bubbles, etc. between the film layer with an ink layer, and ceramics etc., only a film layer is peeled or baked. As a result, the ink layer remains on the surface of the ceramic or the like, and painting is performed.
　以下、本発明を実施例に基づき更に具体的に説明する。例中の部及び％は断りがない限り質量基準である。 Hereinafter, the present invention will be described more specifically based on examples. Unless otherwise indicated, parts and% in the examples are based on mass.
　合成例１
　反応容器に、安息香酸（Ｋａｌａｍａ社製）９００ｇ（７．３８モル）、１，２－プロピレングリコール（旭硝子株式会社製）３２２ｇ（４．２４モル）、エステル化触媒としてテトライソプロピルチタネート０．３７３ｇを、温度計、攪拌器、及び還流冷却器を付した内容積２リットルの四ツ口フラスコに仕込み、窒素気流下で攪拌しながら２３０℃まで段階的に昇温し、酸価が２以下になるまで２３０℃で加熱を続け、生成する水を連続的に除去した。反応後、２３０～２００℃で未反応のプロピレングリコールを減圧留去することによって、エステル化合物（Ｙ－１）（酸価０．０２、粘度７５ｍＰａ・ｓ（２５℃））を９４９ｇ得た。 Synthesis example 1
In a reaction vessel, 900 g (7.38 mol) of benzoic acid (manufactured by Kalama), 322 g (4.24 mol) of 1,2-propylene glycol (manufactured by Asahi Glass Co., Ltd.), and 0.373 g of tetraisopropyl titanate as an esterification catalyst. , Charged in a 2 liter four-necked flask equipped with a thermometer, stirrer, and reflux condenser and gradually heated to 230 ° C. while stirring under a nitrogen stream, resulting in an acid value of 2 or less Heating at 230 ° C. was continued until water formed was continuously removed. After the reaction, unreacted propylene glycol was distilled off at 230 to 200 ° C. under reduced pressure to obtain 949 g of ester compound (Y-1) (acid value 0.02, viscosity 75 mPa · s (25 ° C.)).
　合成例２
　反応容器に、安息香酸（Ｋａｌａｍａ社製）７８３ｇ（６．４２モル）、ジエチレングリコール（三菱ケミカル株式会社製）３７４ｇ（３．５３モル）、エステル化触媒としてテトライソプロピルチタネート０．３４７ｇを、温度計、攪拌器、及び還流冷却器を付した内容積２リットルの四ツ口フラスコに仕込み、窒素気流下で攪拌しながら２３０℃まで段階的に昇温し、酸価が２以下になるまで２３０℃で加熱を続け、生成する水を連続的に除去した。反応後、２３０～２００℃で未反応のジエチレングリコールを減圧留去することによって、エステル化合物（Ｙ－２）（酸価０．０２、粘度７７ｍＰａ・ｓ（２５℃））を９４３ｇ得た。 Synthesis example 2
In a reaction vessel, 783 g (6.42 mol) of benzoic acid (manufactured by Kalama), 374 g (3.53 mol) of diethylene glycol (manufactured by Mitsubishi Chemical Corporation), 0.347 g of tetraisopropyl titanate as an esterification catalyst, A four-necked flask with an internal volume of 2 liters equipped with a stirrer and a reflux condenser was charged stepwise to 230 ° C. while stirring under a nitrogen stream, and at 230 ° C. until the acid value became 2 or less. Heating was continued and water formed was continuously removed. After the reaction, 943 g of ester compound (Y-2) (acid number 0.02, viscosity 77 mPa · s (25 ° C.)) was obtained by distilling off unreacted diethylene glycol at 230 to 200 ° C. under reduced pressure.
　合成例３
　反応容器に、安息香酸（Ｋａｌａｍａ社製）７８０ｇ（６．３９モル）、ジプロピレングリコール（旭硝子株式会社製）４７１ｇ（３．５１モル）、エステル化触媒としてテトライソプロピルチタネート０．３７８ｇを、温度計、攪拌器、及び還流冷却器を付した内容積２リットルの四ツ口フラスコに仕込み、窒素気流下で攪拌しながら２３０℃まで段階的に昇温し、酸価が２以下になるまで２３０℃で加熱を続け、生成する水を連続的に除去した。反応後、２３０～２００℃で未反応のジプロピレングリコールを減圧留去することによって、エステル化合物（Ｙ－３）（酸価０．０１、粘度１４０ｍＰａ・ｓ（２５℃））を９５７ｇ得た。 Synthesis example 3
In a reaction vessel, 780 g (6.39 mol) of benzoic acid (manufactured by Kalama), 471 g (3.51 mol) of dipropylene glycol (manufactured by Asahi Glass Co., Ltd.), 0.378 g of tetraisopropyl titanate as an esterification catalyst, a thermometer , Charged in a two-liter four-necked flask equipped with a stirrer and a reflux condenser, gradually heated to 230 ° C. while stirring under a nitrogen stream, and 230 ° C. until the acid value became 2 or less. And the water produced was continuously removed. After the reaction, unreacted dipropylene glycol was distilled off under reduced pressure at 230 to 200 ° C. to obtain 957 g of an ester compound (Y-3) (acid value 0.01, viscosity 140 mPa · s (25 ° C.)).
　合成例４
　反応容器に、アジピン酸（旭化成ケミカルズ社製）３２７ｇ（２．２４）、１，２－プロピレングリコール（旭硝子株式会社製）４０１ｇ（５．２８モル）、安息香酸（Ｋａｌａｍａ社製）５４５ｇ（４．４７モル）、エステル化触媒としてテトライソプロピルチタネート０．１２０ｇを、温度計、攪拌器、及び還流冷却器を付した内容積２リットルの四ツ口フラスコに仕込み、窒素気流下で攪拌しながら２３０℃まで段階的に昇温し、酸価が５以下になるまで２３０℃で加熱を続け、生成する水を連続的に除去した。反応後、２３０～２００℃で未反応の１，２－プロピレングリコールを減圧留去することによって、エステル化合物（Ｙ－４）（酸価０．５、粘度６７２ｍＰａ・ｓ（２５℃））を９８８ｇ得た。 Synthesis example 4
In a reaction vessel, adipic acid (Asahi Kasei Chemicals) 327 g (2.24), 1,2-propylene glycol (Asahi Glass Co., Ltd.) 401 g (5.28 mol), benzoic acid (Kalama Co., Ltd.) 545 g (4. 47 mol), 0.120 g of tetraisopropyl titanate as an esterification catalyst was charged into a 2-liter four-necked flask equipped with a thermometer, a stirrer, and a reflux condenser, and stirred at 230 ° C. under a nitrogen stream. Until the acid value became 5 or less, heating was continued at 230 ° C., and water produced was continuously removed. After the reaction, unreacted 1,2-propylene glycol was distilled off at 230 to 200 ° C. under reduced pressure to obtain 988 g of ester compound (Y-4) (acid value 0.5, viscosity 672 mPa · s (25 ° C.)). Obtained.
　実施例１～４
　重合体（Ｘ）として、三菱ケミカル株式会社製ダイヤナールＢＲ－１１７を１００質量部と、合成例１で得られたエステル化合物（Ｙ）とを、表１に記載の質量部で用い、更に溶剤としてエクソンモービル株式会社製：ソルベッソ１００を１５０質量部中に均一になるよう撹拌混合して、樹脂組成物を調製した。この組成物を、ガラス基板上に０．５０８ｍｍのアプリケーターを用いて製膜し、２５℃×２４時間乾燥後、ガラス基板から剥がし、評価用フィルムを作製した。 Examples 1 to 4
As the polymer (X), 100 parts by mass of Dainal BR-117 manufactured by Mitsubishi Chemical Corporation and the ester compound (Y) obtained in Synthesis Example 1 were used in the parts by mass shown in Table 1, and further a solvent. As ExxonMobil Co., Ltd .: Solvesso 100 was stirred and mixed uniformly in 150 parts by mass to prepare a resin composition. This composition was formed into a film on a glass substrate using a 0.508 mm applicator, dried at 25 ° C. for 24 hours, and then peeled off from the glass substrate to prepare an evaluation film.
　比較例１～２
　実施例において、エステル化合物（Ｙ）の代わりに、フタル酸ジ２－エチルヘキシル（新日本理化株式会社製、サンソサイザーＤＯＰ）を用いる以外は、実施例と同様にしてフィルムを作製した。 Comparative Examples 1 and 2
In the examples, films were prepared in the same manner as in the examples except that di-2-ethylhexyl phthalate (manufactured by Shin Nippon Chemical Co., Ltd., Sunsizer DOP) was used instead of the ester compound (Y).
　＜フィルムの評価方法＞
　引張試験機にて抗張力及び伸度を測定する事で評価した。結果を表１に示す。
　測定機器：株式会社オリエンテック社製「テンシロン万能材料試験機」
　サンプル形状：１０ｍｍ×６０ｍｍ×２０μｍ
　試験速度＝１０ｍｍ／ｍｉｎ
　荷重フルスケール＝１０Ｎ
　チャック間＝２０ｍｍ
　測定雰囲気：温度２３℃、湿度５０％
　上降伏点応力が高く、抗張力の値が高い程、転写紙の強度が優れることを表す。また、引張伸度が大きい程、転写紙の柔軟性が優れることを表す。 <Evaluation method of film>
Evaluation was made by measuring tensile strength and elongation with a tensile tester. The results are shown in Table 1.
Measuring instrument: “Tensilon Universal Material Testing Machine” manufactured by Orientec Co., Ltd.
Sample shape: 10 mm x 60 mm x 20 μm
Test speed = 10 mm / min
Load full scale = 10N
Between chucks = 20 mm
Measurement atmosphere: temperature 23 ° C, humidity 50%
The higher the upper yield stress and the higher the tensile strength value, the better the strength of the transfer paper. In addition, the greater the tensile elongation, the better the flexibility of the transfer paper.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

Claims (8)

  1. 　（メタ）アクリル酸アルキルエステルを必須の原料とする重合体（Ｘ）と、
    下記一般式（１）
    　Ｂ－（Ｇ－Ａ）ｎ－Ｇ－Ｂ　　　　（１）
    　（式中、Ｂは炭素原子数６～１２の芳香族モノカルボン酸の残基であり、Ｇは炭素原子数２～１２のアルキレングリコールの残基または炭素原子数４～１２のオキシアルキレングリコールの残基であり、Ａはジカルボン酸の残基であり、ｎは繰り返し数であって０～３０の整数であり、繰り返しごとにＧ及びＡは同一でも異なっていてもよく、式中に複数あるＢ及びＧは同一でも異なっていても良い。）
    で表されるエステル化合物（Ｙ）と、を含有することを特徴とする転写紙用樹脂組成物。     A polymer (X) having a (meth) acrylic acid alkyl ester as an essential raw material;
    The following general formula (1)
    B- (GA) n -GB (1)
    Wherein B is a residue of an aromatic monocarboxylic acid having 6 to 12 carbon atoms, and G is a residue of an alkylene glycol having 2 to 12 carbon atoms or an oxyalkylene glycol having 4 to 12 carbon atoms. A residue, A is a residue of a dicarboxylic acid, n is the number of repetitions and is an integer of 0 to 30, and G and A may be the same or different for each repetition, and there are a plurality of them in the formula B and G may be the same or different.)
    And an ester compound (Y) represented by the following: a resin composition for transfer paper.
  2. 　前記エステル化合物（Ｙ）の数平均分子量が２００～３０００の範囲である請求項１記載の転写紙用樹脂組成物。 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 3,000.
  3. 　前記一般式（１）中のＢが安息香酸の残基であり、Ｇがエチレングリコール、プロピレングリコール、ジエチレングリコール又はジプロピレングリコールの残基であり、Ａがアジピン酸又はフタル酸の残基である請求項１又は２記載の転写紙用樹脂組成物。 B in said 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 Item 3. The resin composition for transfer paper according to Item 1 or 2.
  4. 　前記エステル化合物（Ｙ）の含有量が、前記重合体（Ｘ）１００質量部に対して３～５０質量部である請求項１～３の何れか１項記載の転写紙用樹脂組成物。 The resin composition for transfer paper according to any one of claims 1 to 3, wherein the content of the ester compound (Y) is 3 to 50 parts by mass with respect to 100 parts by mass of the polymer (X).
  5. 　前記重合体（Ｘ）のガラス転移温度が３０～７０℃の範囲である請求項１～４の何れか１項記載の転写紙用樹脂組成物。 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 ° C.
  6. 　更に、溶剤及びシリカを含有する請求項１～５のいずれか１項記載の転写紙用樹脂組成物。 The resin composition for transfer paper according to any one of claims 1 to 5, further comprising a solvent and silica.
  7. 　更に、ポリシロキサンを含有する請求項１～６の何れか１項記載の転写紙用樹脂組成物。 The resin composition for transfer paper according to any one of claims 1 to 6, further comprising polysiloxane.
  8. 　請求項１～７の何れか１項記載の転写紙用樹脂組成物の乾燥物からなるフィルム層、インキ層、水溶性糊剤層、台紙と、がこの順に積層してなることを特徴とする積層体。 A film layer, an ink layer, a water-soluble glue layer, and a mount made of a dried product of the resin composition for transfer paper according to any one of claims 1 to 7 are laminated in this order. Laminated body.
PCT/JP2019/010504 2018-03-22 2019-03-14 Resin composition for transfer paper and multilayer body WO2019181719A1 (en)

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