JP2000191920A - Thermoplastic resin composition, heat-sensitive tacky sheet and production of heat-sensitive tacky sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition capable of raising a temperature to cause plasticization of a thermoplastic resin, developing sufficient tackiness at a temperature to stick a label and maintaining high adhesiveness and transparency for a long period of time by using both a thermoplastic resin and specific plural solid plasticizers. SOLUTION: This composition comprises (A) a thermoplastic resin and (B) a solid plasticizer composed of (i) a phosphorus compound having 55-100 deg.C melting point and (ii) at least one compound selected from a dioxybenzene derivative and dicyclohexyl phthalate. A compound of the formula (R1 to R4 are each a hydrocarbon or a heterocyclic group; A is a bifunctional hydrocarbon or heterocyclic group; k is 0 or 1; m is 0-3), etc., are preferable as the component i. The dioxybenzene derivative of the component ii is preferably a diester compound of hydroquinone, etc., and an organic monobasic acid. The content of the component B is preferably 30-1,000 pts.wt. based on 100 pts.wt. of the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thermoplastic resin composition, a heat-sensitive adhesive, a heat-sensitive adhesive sheet used for a so-called delayed tack label, and a method for producing the same. Rather, the present invention relates to a thermoplastic resin composition, a heat-sensitive adhesive, a heat-sensitive adhesive sheet, and a method for producing the same, which exhibit adhesiveness when heated.

[0002]

2. Description of the Related Art Conventionally, as a label to be applied to a container such as a bottle or a PET bottle, a glue label is applied to a label substrate at the same time as an adhesive is applied, or an adhesive and a release paper are applied to the label substrate. Are sequentially used.

[0003] However, glue labels require much trouble such as management of the viscosity of the pressure-sensitive adhesive and cleaning of a machine for applying the pressure-sensitive adhesive. Also,
Since a large amount of release paper peeled off from the label is generated as garbage, the pressure-sensitive adhesive label on which the release paper is formed is troublesome, and it is not preferable from the viewpoint of resource saving.

As a label for solving such a problem,
What is called a delayed tack label is known. Delayed tack labels are non-adhesive at room temperature, but a layer of a heat-sensitive adhesive that develops adhesiveness upon heating is formed on a label substrate, and no release paper is required.
Moreover, it has an advantage that it can be easily attached to a container only by heating. Delayed tack labels are usually formed by dispersing solid plasticizer particles and, if necessary, tackifier particles in a binder resin layer having a glass transition temperature of about 0 to 30 ° C., and melting the solid plasticizer by heating. Thereby, the binder resin is plasticized to exhibit adhesiveness. As the solid plasticizer, for example, dicyclohexyl phthalate is well known (JP-A-61-9479, JP-A-7-278521, JP-A-7-145352, JP-A-8-33).
No. 3565).

[0005] The delayed tack label as described above,
In recent years, the emulsion-type heat-sensitive adhesive is often applied to the back surface of a substrate and then subjected to a heating step for drying. The heating temperature in that case is required to be a low temperature of 45 ° C. or less so that dicyclohexyl phthalate does not melt and develop adhesiveness at the stage of forming the adhesive layer. However, such low-temperature heating requires a long time for the heating and drying step, and thus has a problem that the productivity of the delayed tack label is reduced. In addition, since the delayed tack label does not use release paper as described above, if it is stored in a stacked state for a long time at a high temperature in summer, for example, the plasticization of the binder resin by dicyclohexyl phthalate gradually occurs, and the labels are separated from each other. So-called blocking which adheres to each other occurs.
For this reason, there is a problem that a cooling device for preventing such blocking is required. Further, the conventional delayed tack label has a problem that the adhesive strength and the transparency are lost in a short period of time.

JP-A-8-325535 discloses that dicyclohexyl phthalate having an average particle diameter of 4 μm or less is used as a solid plasticizer in order to improve blocking resistance.
There is disclosed a heat-sensitive adhesive sheet using a solid plasticizer such as N-cyclohexyl-p-toluenesulfonamide having a melting point of 70 ° C. or more and an average particle diameter of 4 to 10 μm in combination. Japanese Patent Application Laid-Open No. 9-67551 discloses that as a solid plasticizer, 25 ° C.
It has been proposed to use two or more solid benzenedicarboxylates. Further, Japanese Patent Application Laid-Open No. 9-1698
No. 70 discloses a crystallization retarder such as tribenzyl trimellitate in order to improve the balance between blocking resistance and adhesiveness of a conventional heat-sensitive delayed tack-type tacky thermoplastic resin composition. I have. However, even if these solid plasticizers and crystallization retarders are used, a sufficiently satisfactory result cannot be obtained in terms of blocking resistance, adhesive strength and persistence of transparency.

[0007]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a heat-sensitive adhesive sheet which can be heated and dried at a higher temperature while producing a heat-sensitive adhesive sheet. It is an object of the present invention to provide a thermoplastic resin composition and a heat-sensitive adhesive which can maintain durability and transparency for a long period of time and have excellent blocking resistance. Another object of the present invention is to provide a heat-sensitive pressure-sensitive adhesive sheet having high productivity, excellent adhesiveness and transparency and excellent persistence thereof, and which does not cause blocking even after long-term storage, and a method for producing the same. is there.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to achieve the above object, and as a result, when two or more specific solid plasticizers are used in combination, the temperature at which plasticization of a thermoplastic resin starts to occur is increased. The present inventors have found that not only a sufficient tackiness can be exhibited at the labeling temperature but also high adhesiveness and transparency can be maintained for a long period of time, and the present invention has been completed.

That is, the present invention provides a thermoplastic resin composition containing a thermoplastic resin and a solid plasticizer, wherein the solid plasticizer comprises (i-1) a phosphorus compound having a melting point of 55 to 100 ° C., ii) (ii-1) a dioxybenzene derivative and (ii)
-2) A thermoplastic resin composition characterized by comprising at least one compound selected from dicyclohexyl phthalate.

The present invention also provides a thermoplastic resin composition containing a thermoplastic resin and a solid plasticizer, wherein the solid plasticizer comprises (i-2) the following formulas (1a), (1b), (1 1c) or (2)

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ^1a , R ^3a , R ^4a ,
R ⁵ , R ⁶ and R ⁷ each represent a hydrocarbon group or a heterocyclic group; A represents a divalent hydrocarbon group or a heterocyclic group;
Represents 0 or 1, and n represents an integer of 1 to 3. Where R
^1a , R ^3a and R ^4a are not simultaneously a phenyl group or a 4-t-butylphenyl group. R ¹ and R ² and A, R ³ and R ⁴ and A, R ¹ and R ³ R ^1a and R ^3a and R ^4a in the formula (1b), in the formula (1c) and R ⁴ in Formula (1a), formula R ⁵ , R ^6, and R ⁷ in (2) may be two or more groups bonded to each other to form a ring containing a phosphorus atom), and (ii) (ii- 1) A thermoplastic resin composition characterized by comprising a dioxybenzene derivative and (ii-2) at least one compound selected from dicyclohexyl phthalate.

[0011] The present invention also provides a heat-sensitive adhesive containing the above-mentioned thermoplastic resin composition. The present invention further provides a heat-sensitive adhesive sheet having at least one surface of a substrate provided with an adhesive layer composed of the above-mentioned heat-sensitive adhesive.

The present invention further provides a method for producing a heat-sensitive adhesive sheet, in which at least one surface of a substrate is coated with the above-mentioned heat-sensitive adhesive to form an adhesive layer.

[0013]

Embodiments of the present invention will be described below. The thermoplastic resin composition of the present invention contains a thermoplastic resin as a binder resin and a solid plasticizer.

Examples of the thermoplastic resin include, for example, homo- or copolymers of (meth) acrylate, styrene- (meth) acrylate copolymer, and vinyl acetate.
(Meth) acrylate copolymer, ethylene- (meth) acrylate copolymer, ethylene- (meth)
Acrylic acid copolymer, (meth) acrylic acid ester-
(Meth) acrylic acid copolymer, styrene-acrylonitrile- (meth) acrylic acid ester copolymer, styrene- (meth) acrylic acid ester- (meth) acrylic acid copolymer, styrene-acrylonitrile- (meth) acrylic acid Ester- (meth) acrylic acid copolymer, ethylene-vinyl acetate- (meth) acrylic acid ester copolymer,
Acrylic polymers containing (meth) acrylic acid or its ester as a monomer, such as vinylpyrrolidone- (meth) acrylic acid ester copolymer and styrene-butadiene- (meth) acrylic acid copolymer; vinyl acetate resin; Vinyl acetate polymers containing vinyl acetate as a monomer such as ethylene-vinyl acetate copolymer; styrene-butadiene copolymer, isobutylene resin, isobutylene-isoprene copolymer, butadiene resin, styrene-isoprene copolymer, Synthetic rubber such as acrylonitrile-butadiene copolymer; natural rubber; ethylene-vinyl chloride copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl virolidone-
Examples include a styrene copolymer, a chlorinated propylene resin, a urethane resin, and ethyl cellulose. These thermoplastic resins may be used alone or in combination of two or more.

Preferred thermoplastic resins include acrylic polymers [eg, acrylic copolymers containing (meth) acrylic acid ester as a monomer], vinyl acetate polymers,
Synthetic rubber, natural rubber and the like are included. Among the acrylic polymers, particularly, acrylate-methacrylate copolymers (for example, C _2-10 alkyl acrylate-C _1-4 alkyl methacrylate copolymers), acrylate-methacrylate Acid ester
(Meth) acrylic acid copolymer (for example, acrylic acid C
_2-10 alkyl ester-methacrylic acid C _1-4 alkyl ester- (meth) acrylic acid copolymer), acrylate ester-styrene- (meth) acrylic acid copolymer (for example, C _2-10 alkyl acrylate) -Styrene-
Acrylics containing (meth) acrylic acid copolymer) or another acrylate (for example, C _2-10 alkyl acrylate) and methacrylate (for example, C _1-4 alkyl methacrylate) or styrene as a comonomer. A copolymer is preferred.

Glass transition temperature (Tg) of thermoplastic resin
Can be appropriately selected in consideration of the type of the adherend and the like in a range that does not impair the adhesiveness and the blocking resistance in the case of a pressure-sensitive adhesive sheet, and is usually about -10 to 70 ° C. When the glass transition temperature is lower than −10 ° C., the blocking resistance tends to decrease. On the other hand, if the glass transition temperature is too high, the adhesiveness tends to decrease.

In the present invention, the solid plasticizer comprises (i-1)
It is composed of a phosphorus compound having a melting point of 55 to 100 ° C. and at least one compound selected from (ii) (ii-1) a dioxybenzene derivative and (ii-2) dicyclohexyl phthalate.

The phosphorus compound (i-1) includes phosphoric esters, phosphites, phosphines and the like.

As a preferred phosphorus compound, the following formula (1)
Or (2)

Embedded image (Wherein, R ^{1 to} R ⁷ each represent a hydrocarbon group or a heterocyclic group, A represents a divalent hydrocarbon group or a heterocyclic group,
k represents 0 or 1, and m represents an integer of 0 to 3. R ¹ , R ² and A (when m = 1 to 3), R ³ , R ⁴ and A (m = 1
, R ¹ , R ^3, and R ⁴ (when m = 0), R ⁵ , R ^6, and R ⁷ form a ring containing a phosphorus atom by bonding of two or more groups to each other. Or a compound represented by the formula: The compounds represented by the formula (1) include the following formulas (1a), (1b) and (1c)

Embedded image (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ^1a , R ^3a , R ^4a ,
R ⁵ , R ⁶ and R ⁷ each represent a hydrocarbon group or a heterocyclic group; A represents a divalent hydrocarbon group or a heterocyclic group;
Represents 0 or 1, and n represents an integer of 1 to 3. Where R
^1a , R ^3a and R ^4a are not simultaneously a phenyl group or a 4-t-butylphenyl group. R ¹ and R ² and A in the formula (1a), R ³ and R ⁴ and A, R ^1a in formula (1b) and R ^3a and R ^4a, R ¹ and R ³ and R ⁴ in the formula (1c) is, 2 each
(The above groups may combine with each other to form a ring containing a phosphorus atom).

The hydrocarbon groups represented by R ^{1 to} R ⁷ , R ^1a , R ^3a and R ^4a include aromatic hydrocarbon groups, alicyclic hydrocarbon groups and aliphatic hydrocarbon groups. These hydrocarbon groups may have a substituent.

Examples of the aromatic hydrocarbon group include phenyl and naphthyl groups. The alicyclic hydrocarbon group includes cycloalkyl groups such as cyclopentyl, cyclohexyl and cyclooctyl groups; cycloalkenyl groups such as cyclopentenyl and cyclohexenyl groups; norbornyl, bicyclo [4.3.0] nonyl, adamantyl groups and the like. And a crosslinked ring hydrocarbon group. Examples of the aliphatic hydrocarbon group include alkyl groups having about 1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, octyl, and decyl; vinyl, allyl, An alkenyl group having about 2 to 12 carbon atoms such as a 1-hexenyl group; an alkynyl group having about 2 to 12 carbon atoms such as an ethynyl and propynyl group;

Examples of the substituent which the hydrocarbon group may have include, for example, halogen atoms such as fluorine, chlorine and bromine atoms; methyl, ethyl, propyl, isopropyl,
C _1-4 alkyl groups such as isobutyl, s-butyl and t-butyl groups; cycloalkyl groups such as cyclohexyl groups;
Aryl groups such as phenyl groups; C _1-4 alkoxy groups such as methoxy, ethoxy and isopropoxy groups; aryloxy groups such as phenyloxy groups; C _1-4 alkoxycarbonyl groups such as methoxycarbonyl groups; acetyl and benzoyl groups Acyloxy group such as acetyloxy group; cyano group; nitro group; hydroxyl group; carboxyl group; oxo group and the like.

Representative examples of the aromatic hydrocarbon group include a phenyl group; a phenyl group having a halogen atom such as 2-chlorophenyl, 3-chlorophenyl, and 4-chlorophenyl group; 2-methylphenyl, 3-methylphenyl; 4-methylphenyl, 2,3-dimethylphenyl,
Examples include a phenyl group having a C _1-4 alkyl group such as a 2,4-dimethylphenyl, 2,6-dimethylphenyl, 2-ethylphenyl, and 4-t-butylphenyl group. Representative examples of the alicyclic hydrocarbon group include cyclopentyl, cyclohexyl, cyclohexenyl,
3,5-trimethylcyclohexyl, 3-oxo-1,
5,5-trimethylcyclohexyl, 6-oxo-2,
4,4-trimethyl-1-cyclohexenyl, 1,7,
And a 7-trimethylnorbornan-2-yl group. Representative examples of the aliphatic hydrocarbon group include an alkyl group (aralkyl group) to which an aryl group such as benzyl, 2-methylphenylmethyl, and 2-phenylethyl is bonded.

The heterocyclic group represented by R ^{1 to} R ⁷ , R ^1a , R ^3a and R ^4a includes an oxygen atom-containing heterocyclic group such as 2-furyl, morphonyl and tetrahydropyranyl; 2-thienyl And a nitrogen atom-containing heterocyclic group such as a 1-pyrrolyl, 2-pyridyl, piperidino and 2-quinolyl group. These heterocyclic groups may have a substituent. Examples of the substituent include the substituents exemplified for the hydrocarbon group.

The divalent hydrocarbon group in the above A has 2
Divalent aromatic hydrocarbon group, divalent alicyclic hydrocarbon group and
Valent aliphatic hydrocarbon groups. Two or more of these hydrocarbon groups may be bonded via or without a linking group such as an oxygen atom, a sulfur atom, a carbonyl group, and a carbonyloxy group, and may have a substituent. Examples of the substituent include the groups exemplified as the substituent which the hydrocarbon group in R ^{1 to} R ^{7 and the} like may have.

As the divalent aromatic hydrocarbon group, for example,
Examples thereof include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, and biphenylene. Cycloalkylidene such as cyclohexylidene, 1,2-cyclopentylene, 1,2-cyclohexylene, 1,3-cyclohexylene, 1,4-cyclohexylene as a divalent alicyclic hydrocarbon group; Groups; cycloalkenylene groups such as 2-cyclohexene-1,4-diyl group; and divalent bridged cyclic groups such as adamantane-1,3-diyl group. The divalent aliphatic hydrocarbon group includes an alkylene group having about 1 to 6 carbon atoms such as methylene, ethylene, trimethylene, 2-methyltrimethylene, 2,2-dimethyltrimethylene, and tetramethylene; a propenylene group Alkenylene groups having about 2 to 6 carbon atoms; alkynylene groups having about 2 to 6 carbon atoms such as propynylene groups;

Representative examples of the divalent hydrocarbon group in the above A include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, and 1,1-phenylene.
-Diphenylethane-4 ', 4 "-diyl, 2,2-diphenylpropane-4', 4" -diyl, 2,2-diphenylbutane-4 ', 4 "-diyl, 4,4'-biphenylene, , 4-cyclohexylene, 1,5,5-trimethylcyclohexane-1,3-diyl, 6-oxo-
2,4,4-trimethylcyclohexane-1,2-diyl, -CH ₂ -1,4-cyclohexylene-CH _2- ,
1,1-dicyclohexylethane-4 ', 4 "-diyl, 2,2-dicyclohexylpropane-4', 4"-
Diyl, 2,2-dicyclohexylbutane-4 ', 4 "
-Diyl, adamantane-1,3-diyl, 5,7-dimethyladamantane-1,3-diyl, trimethylene,
Examples include 2-methyltrimethylene, 2,2-dimethyltrimethylene, and tetramethylene groups.

The divalent heterocyclic group in the above A is a divalent heterocyclic alcohol or phenol (for example, saccharides such as isosorbide, isomannide, sucrose, lactose, etc.) from which two hydroxyl groups are removed. Groups are included. Two or more of these hydrocarbon groups may be bonded via or without a linking group such as an oxygen atom, a sulfur atom, a carbonyl group, and a carbonyloxy group, and may have a substituent. Examples of the substituent include the groups exemplified as the substituent which the hydrocarbon group in R ^{1 to} R ^{7 and the} like may have. Further, the divalent hydrocarbon group and the divalent heterocyclic group may be bonded via the above-mentioned linking group or not.

[0029] In the above formula (1a), at least one of R ¹ to R ⁴ (in particular, all R ¹ to R ⁴⁾ preferably is an aromatic hydrocarbon group. Preferred A includes 1,3
- at least divalent alicyclic hydrocarbon such groups - a divalent hydrocarbon group, xylene -CH ₂ to -CH _2-1,4-cyclo comprising at least divalent aromatic hydrocarbon base, such as a phenylene group A divalent hydrocarbon group containing a base is included. n
Is preferably 1 or 2, especially 1.

Specific examples of the phosphorus compound represented by the formula (1a) include, for example, 1,4-cyclohexanedimethanol bis (diphenyl phosphate) (melting point: 97 ° C.), resorcinol bis [di (2,6-dimethylphenyl) ) Phosphate] (melting point: 95 ° C.).

Preferred compounds represented by the above formula (1b) include compounds in which R ^1a , R ^3a and R ^4a are each an aromatic hydrocarbon group or an aralkyl group, and compounds of R ^1a , R ^3a and R ^4a . Among them, cyclic phosphates in which two or more groups are bonded to each other to form a ring containing a phosphorus atom, and the like are included.

Specific examples of the compound (phosphate ester) represented by the formula (1b) include, for example, phosphorus such as tri (methylphenyl) phosphate such as tri (4-methylphenyl) phosphate (melting point: 78 ° C.). Acid triaryl esters, tribenzyl phosphate (melting point: 65 ° C)
Triaralkyl phosphates such as the following formula (3)

Embedded image (Melting point: 95 to 110 ° C.), and cyclic phosphates containing a phosphorus atom as a ring constituent atom.

In the formula (1c), each of R ^{1 to} R ⁴ is preferably an aromatic hydrocarbon group or an aralkyl group.

Specific examples of the compound represented by the formula (1c) (phosphites) include, for example, triaryl phosphite such as tri (4-t-butylphenyl) phosphite (melting point: 75 ° C.) Esters and the like.

In the above formula (2), R ^{5 to} R ⁷ are preferably an aromatic hydrocarbon group. Specific examples of the compound represented by the formula (2) include, for example, triarylphosphines such as triphenylphosphine (melting point: 80 ° C.) and tri (3-methylphenyl) phosphine (melting point: 100 ° C.).

The above phosphorus compound can be obtained by a known or known method. For example, phosphates are
Phosphorus oxychloride, dichlorophosphate monoester such as aryldichlorophosphate, or chlorophosphate diester such as diarylchlorophosphate, and a hydroxyl group-containing compound (alcohol or phenol) corresponding to the target compound, if necessary, a base such as pyridine By reacting in the presence of In addition, cyclic phosphates containing a phosphorus atom as a constituent atom of a ring include, as the hydroxyl group-containing compound, a divalent or higher, preferably trivalent or higher (eg, trivalent or tetravalent) hydroxyl group-containing compound [eg, 1 , 1,1-tris (hydroxymethyl) ethane, pentaerythritol, etc.].

The phosphites can be produced, for example, by reacting phosphorus trichloride with an alcohol or phenol corresponding to the target compound in the presence of a base, if necessary. Further, phosphines (such as triphenylphosphine) can be obtained, for example, by reacting phosphorus trichloride with a Grignard reagent (such as phenylmagnesium bromide) corresponding to the target compound.

The melting point of the phosphorus compound represented by the formula (1a), (1b), (1c) or (2) is not necessarily limited to the range of 55 to 100 ° C.
It may be about 160 ° C, preferably about 55 to 105 ° C. If the melting point is too low, the blocking resistance tends to decrease. Conversely, if the melting point is too high, it takes a long time to melt, and there is a possibility that the productivity may decrease or the base material may be deteriorated.
The phosphorus compounds (i-1) can be used alone or in combination of two or more.

The dioxybenzene derivative (ii-1) includes hydroquinone, resorcinol, catechol and derivatives thereof. Examples of the derivative include an alkyl-substituted product in which a benzene ring is substituted with 1 to 4 alkyl groups such as a methyl group, and a mono- or diether compound in which at least one hydroxyl group of two hydroxyl groups is etherified (for example, Mono- or di-alkyl ethers such as methyl ether, mono- or di-aryl ethers such as phenyl ether, etc.) and mono- or di-esters in which at least one of the two hydroxyl groups is esterified (for example, fat such as acetic acid ester) Aromatic carboxylic acid mono- or diesters, such as benzoic acid esters, etc.). In the ether form and the ester form, the benzene ring may be substituted with a substituent such as an alkyl group such as a methyl group.

Preferred dioxybenzene derivatives include:
(A) a diester compound of (A1) hydroquinone or resorcinol whose benzene ring may be substituted with an alkyl group, or (A2) a catechol having a benzene ring substituted with an alkyl group, and (B) an organic monobasic acid; included.

The alkyl group includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s
And alkyl groups having about 1 to 6 carbon atoms, such as -butyl, t-butyl, pentyl and hexyl groups. Among them, an alkyl group having about 1 to 4 carbon atoms such as a methyl group is preferable. The number of substitution of the alkyl group on the benzene ring in hydroquinone or resorcinol is 0 or 1 to 4 (preferably 1 to 3, more preferably 2 or 3).
Further, the number of substitution of the alkyl group on the benzene ring of catechol is 1 to 4, preferably 1 to 3, and more preferably 2 or 3. When the number of substitution of the alkyl group is plural, the alkyl groups may be the same or different.

In the component (A), a substituent other than an alkyl group may be bonded to the benzene ring. Examples of such a substituent include halogen atoms such as fluorine, chlorine and bromine atoms; hydroxyl groups; alkoxy groups such as methoxy and ethoxy groups (eg C _1-4 alkoxy groups); aryloxy groups such as phenoxy groups; Acyloxy groups such as acetyloxy, propionyloxy and benzoyloxy groups; acyl groups such as acetyl, propionyl and benzoyl groups; carboxyl groups; alkoxycarbonyl groups such as methoxycarbonyl and ethoxycarbonyl groups; cyano groups; The benzene ring may be condensed with a 3- to 8-membered aromatic or non-aromatic carbon or heterocyclic ring such as a cyclopentane ring, a cyclohexane ring, a benzene ring, and a tetrahydrofuran ring.

Examples of the (A1) hydroquinone or resorcinol in which the benzene ring may be substituted with an alkyl group include, for example, hydroquinone, methylhydroquinone, 2,3-dimethylhydroquinone, 2,5-dimethylhydroquinone, and 2,6-dimethylhydroquinone. Dimethylhydroquinone, trimethylhydroquinone, resorcinol, 4-
Methyl resorcinol, 5-methyl resorcinol,
Examples thereof include 2,5-dimethylresorcinol, 4,6-dimethylresorcinol, and 2,4,6-trimethylresorcinol. Examples of (A2) catechol in which the benzene ring is substituted with an alkyl group include 3-methylcatechol, 4-methylcatechol, and trimethylcatechol.

The organic monobasic acid (B) includes aliphatic, alicyclic, aromatic or heterocyclic monobasic acids (such as carboxylic acids and sulfonic acids). Of these, aliphatic, alicyclic or aromatic monocarboxylic acids are preferred.

Examples of the aliphatic monocarboxylic acids include aliphatic monocarboxylic acids having about 1 to 6 carbon atoms, such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, and pivalic acid. Is an aliphatic monocarboxylic acid having about 1 to 4 carbon atoms, especially acetic acid). Examples of the alicyclic monocarboxylic acid include a cycloalkanecarboxylic acid having about 3 to 8 members such as cyclopentanecarboxylic acid and cyclohexanecarboxylic acid. Aromatic carboxylic acids include, for example, benzoic acid, toluic acid, naphthoic acid, etc., in which an aromatic ring has an alkyl group (such as an alkyl group having about 1 to 4 carbon atoms) and an alkoxy group (an alkoxy group having about 1 to 4 carbon atoms). ), Halogen atoms (fluorine, chlorine,
Aromatic carboxylic acids which may have one or more substituents such as a bromine atom).

As a typical example of the diester compound, hydroquinone diacetate (melting point: 123
° C), trimethylhydroquinone diacetate (melting point:
109 ° C.), 3,4,5-trimethylcatechol diacetate (melting point: 120 ° C.) and the like.

The diester compound is obtained by, for example, combining the component (A) with the component (B) an organic monobasic acid or a reactive derivative thereof (eg, acid halide, active ester, acid anhydride, etc.), if necessary. It can be obtained by reacting according to a known esterification method in the presence of an acid catalyst or a base.

A diester compound of 3,4,5-trimethylcatechol and an organic monobasic acid can be prepared in the presence of an acid catalyst in the presence of 2,6,6-trimethylcyclohex-2-ene-
It can be obtained by reacting 1,4-dione (ketoisophorone) with an acylating agent (acid anhydride, acyl halide, enol ester, etc.) corresponding to the organic monobasic acid.

In this method, as the acid catalyst, a professional
Either tonic acid or Lewis acid can be used. As a protonic acid
And super strong acid (SbF_Five, SbF_Five-HF, SbF_Five-FS
O_ThreeH, SbF_Five-CF_ThreeSO_ThreeH, etc.), sulfuric acid, hydrochloric acid,
Acid, fluoboric acid, p-toluenesulfonic acid,
Organic and inorganic acids such as acetic acid, picric acid, and heteropoly acids
Acids. As the Lewis acid, for example, BF
_Three, BF_ThreeO (C_TwoH_Five) _Two, AlCl_Three, FeCl_Threeetc
Can be illustrated. The amount of these catalysts used is, for example,
0.001 to 20 mol% with respect to sophorone, preferably
Is about 0.01 to 15 mol%.

Further, a solid acid catalyst can be used as the acid catalyst. Solid acid catalysts include strongly acidic ion-exchange resins [for example, styrene divinylbenzene sulfonic acid-based ion-exchange resins such as Amberlyst 15 (manufactured by Organo Corporation)]; super-strongly acidic resins [for example, Nafion NR5
0 (manufactured by Aldrich) and the like]; aluminosilicates such as zeolite and silica-alumina or inorganic oxides (including composite oxides); carriers (eg, graphite, metal sulfate, metal chloride) , Activated carbon, ion-exchange resin, zeolite, alumina, silica, silica-alumina, silica-titania, silica-zirconia, titania-zirconia, kaolin, etc .; Catalyst and the like. The amount of solid acid catalyst used is
For example, it is about 0.1 to 1000% by weight, preferably about 5 to 100% by weight, based on ketoisophorone.

The amount of the acylating agent used is, for example, 2 mol or more, preferably 3 mol, per mol of ketoisophorone.
About 10 mol. An acylating agent may be used as a solvent.

The reaction between the ketoisophorone and the acylating agent is as follows:
The reaction may be performed without a solvent or in a solvent. Examples of the solvent include hydrocarbons such as hexane, octane, octene, cyclohexane, cyclohexene, benzene, toluene, and xylene; carboxylic acids such as acetic acid and propionic acid; methylene chloride, 1,2-dichloroethane, chlorobenzene, and dichlorobenzene. Halogenated hydrocarbons; ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether; ketones such as acetone and methyl ethyl ketone; amides such as N, N-dimethylformamide and N-methylpyrrolidone. Can be

The reaction temperature when reacting the ketoisophorone with the acylating agent is, for example, 0 to 150 ° C., preferably 1 to 150 ° C.
It is about 0 to 100 ° C. The resulting diester compound can be separated and purified by subjecting it to conventional separation and purification means such as filtration, concentration, extraction, recrystallization, and column chromatography.

The thus obtained diester compound of 3,4,5-trimethylcatechol and an organic monobasic acid is reacted with an acid such as the above-mentioned protonic acid or solid acid catalyst.
By reacting with water, 3,4,5-trimethylcatechol can be obtained. In this case, the water is usually
It is used in excess with respect to the diester compound. The reaction temperature in this hydrolysis reaction is, for example, about 40 to 100 ° C. The generated 3,4,5-trimethylcatechol can be isolated, for example, by the above-mentioned separation and purification means.

The dioxybenzene derivative (ii-1) includes, for example, catechol, catechol diacetate, catechol dibenzoate, catechol monophenyl ether,
Catechol diphenyl ether and the like are also included.

The melting point of the dioxybenzene derivative (ii-1) may be, for example, about 50 to 160 ° C., but is preferably about 90 to 130 ° C. If the melting point of the dioxybenzene derivative (ii-1) is too low, the blocking resistance tends to decrease. Conversely, if the melting point is too high, it takes a long time to melt, thereby lowering productivity or deteriorating the base material. There is a risk. The dioxybenzene derivative (ii-1) can be used alone or in combination of two or more.

In the present invention, as the component (ii) constituting the solid plasticizer, at least (ii-1) a dioxybenzene derivative of the above (ii-1) dioxybenzene derivative and (ii-2) dicyclohexyl phthalate It is preferable to use

In the present invention, (i) (i-1) a phosphorus compound having a melting point of 55 to 100 ° C. or (i-2) a compound of the formula (1)
a) a phosphorus compound represented by (1b), (1c) or (2), (ii) (ii-1) a dioxybenzene derivative and (ii-
2) The ratio with at least one compound selected from dicyclohexyl phthalate is not particularly limited. For example, compound (i) / compound (ii) (weight ratio) = 1/9
9-99 / 1, preferably 5 / 95-95 / 5, more preferably 10 / 90-90 / 10, especially 20 / 80-
It is about 80/20 (for example, 30/70 to 70/30).

In the present invention, the content of the solid plasticizer is
For example, 30 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin
00 parts by weight, preferably 100 to 1000 parts by weight, more preferably 150 to 900 parts by weight, especially 200 to 80 parts by weight
It is about 0 parts by weight. If the content of the solid plasticizer is less than 30 parts by weight, sufficient tackiness may not be exhibited at the time of heating, and if the content is more than 1000 parts by weight, cohesive strength may be reduced and sufficient adhesive strength may not be exhibited. There is.

Since the thermoplastic resin composition of the present invention contains a plurality of specific solid plasticizers as described above, it has a high temperature at which tackiness is exhibited, and melts and easily plasticizes at the label sticking temperature. In addition, the recrystallization of the solid plasticizer is delayed, and high transparency and adhesion are maintained for a long time.

In the present invention, a solid plasticizer other than those described above may be used together if necessary, as long as the effects of the present invention are not impaired. Other solid plasticizers that can be used in combination include, for example, phthalic esters such as diphenyl phthalate, dihexyl phthalate, diisohexyl phthalate, and dinaphthyl phthalate; dimethyl isophthalate, dibenzyl isophthalate,
Isophthalic esters such as didicyclohexyl isophthalate; terephthalic esters such as dimethyl terephthalate, dibenzyl terephthalate and didicyclohexyl terephthalate; sucrose benzoate, ethylene glycol dibenzoate, trimethylolethane tribenzoate, and tribenzoic acid Examples include glyceride, pentaerythroate tetrabenzoate, sucrose octaacetate, tricyclohexyl citrate, N-cyclohexyl-p-toluenesulfonamide, urea derivatives, paraffin chloride and the like.

The thermoplastic resin composition of the present invention may contain a tackifier as required. Examples of the tackifier that can be used include terpene resins, aliphatic petroleum resins, aromatic petroleum resins, cumarone-indene resins, styrene resins, phenol resins, terpene-phenol resins, rosin derivatives (rosin, polymerized rosin) , Hydrogenated rosins and their esters with glycerin, pentaerythritol, etc., resin acid dimers, etc.), and resins such as xylene resins. Two or more of these tackifiers may be used in combination.

Although the content of the tackifier is not particularly limited, it can be appropriately selected according to the combination of the thermoplastic resin and the solid plasticizer. Usually, 10 to 10 parts by weight of the thermoplastic resin is used. About 600 parts by weight, 20 to 50 parts
About 0 parts by weight is preferable.

The thermoplastic resin composition of the present invention may contain, in addition to the tackifier described above, conventional additives such as an antifoaming agent, a coating improver, a thickener, a lubricant, as long as the properties are not impaired. Stabilizers (antioxidants, ultraviolet absorbers, heat stabilizers, etc.), antistatic agents, antiblocking agents (inorganic particles, organic particles, etc.)
May be added.

The thermoplastic resin composition of the present invention may be an aqueous composition obtained by dispersing a thermoplastic resin in water using a dispersant. The dispersant that can be used is not particularly limited, and any of conventionally known anionic and nonionic dispersants can be used. Examples of the anionic dispersant include a carboxylate, a sulfate, a sulfonate, and a phosphate, and among them, ammonium carboxylate is preferable. Nonionic dispersants include polyethylene glycol type,
Polyhydric alcohol type and the like can be mentioned.

As the method of preparing the aqueous composition, various conventionally known methods can be employed. For example, as the above-mentioned preparation method, a method in which the components constituting the thermoplastic resin composition of the present invention are preliminarily mixed and then dispersed in water, and after dispersing a solid plasticizer in a thermoplastic resin emulsion or a tackifier emulsion, And a method in which a solid plasticizer is dispersed in water, and a thermoplastic resin emulsion and a tackifier emulsion are mixed with the dispersion. Examples of the method of dispersing the solid plasticizer in the above-mentioned emulsion or water include a method of dispersing a molten solid plasticizer, a method of dispersing a solid plasticizer while making it into a fine powder, and a method of dispersing a solid plasticizer that is made into a fine powder. Can be exemplified.

The thermoplastic resin emulsion may be prepared by emulsion polymerization. Alternatively, after a polymer is obtained by a method other than emulsion polymerization, it is emulsified by using additives as necessary. You may. For example,
An additive (eg, emulsifier, pH adjuster, acid, etc.) is added to an organic solution containing a polymer polymerized in the presence of a water-soluble organic solvent (eg, alcohol such as isopropyl alcohol), and then water is added. Then, by emulsifying, and then removing the organic solvent, a thermoplastic resin emulsion can be prepared.

The average particle size of the solid plasticizer in the aqueous composition is preferably about 0.5 to 20 μm, and more preferably about 1 to 15 μm. Average particle size 0.5
If the particle size is smaller than μm, the blocking resistance may decrease, or the pulverization may require time to lower the productivity. If the average particle size exceeds 20 μm, the coated surface may be rough and the quality of the label may be degraded.

The thermoplastic resin composition of the present invention can be used as a heat-sensitive adhesive. By forming a heat-sensitive adhesive layer (adhesive layer) on at least one surface of a substrate, the heat-sensitive adhesive can be used. The adhesive sheet is obtained. The layer of the heat-sensitive adhesive is applied by dissolving the heat-sensitive adhesive in an organic solvent,
It can be formed by applying heat and melting. In addition, an aqueous composition in which a thermoplastic resin is dispersed in water can be applied to at least one surface of a substrate and dried to form a heat-sensitive adhesive sheet. Examples of the coating method include a method using a roll coater, an air knife coater, a blade coater, a rod coater, a bar coater, a comma coater, a gravure coater, a silk screen coater, and the like.

As the base material for forming the heat-sensitive adhesive layer, paper, coated paper, plastic film, wood, cloth,
Nonwoven fabrics, metals and the like can be mentioned. Examples of the polymer constituting the plastic film include polyolefins such as polyethylene and polypropylene, ethylene-vinyl acetate copolymer, polyvinyl chloride, and vinyl chloride-
Vinyl acetate copolymer, poly (meth) acrylate, polystyrene, polyvinyl alcohol, ethylene-
Vinyl alcohol copolymers, cellulose derivatives such as cellulose acetate, polyesters (polyalkylene terephthalates such as polyethylene terephthalate and polybutylene terephthalate, polyalkylene naphthalates such as polyethylene naphthalate and polybutylene naphthalate),
Polycarbonate, polyamide (polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 6/12
And the like, polyester amide, polyether, polyimide, polyamide imide, polyether ester, and the like. Further, copolymers, blends, and crosslinked products thereof may be used.

[0071]

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples. The average particle size of the solid plasticizer was measured using a laser diffraction particle size distribution analyzer (LA-500, manufactured by HORIBA, Ltd.)
The median diameter was described.

Preparation Example 1 (Preparation of aqueous dispersion of solid plasticizer 1) 100 parts by weight of resorcinol bis [di (2,6-dimethylphenyl) phosphate] (melting point: 95 ° C.) as a solid plasticizer and an anionic dispersant By mixing 15 parts by weight of a surfactant (polycarboxylic acid ammonium salt) and 80 parts by weight of water and pulverizing the mixture with a ball mill until the average particle diameter becomes 2.6 μm, resorcinol bis [di (2,6- Dimethylphenyl) phosphate] (solid plasticizer aqueous dispersion 1).

Preparation Example 2 (Preparation of aqueous dispersion of solid plasticizer 2) As a solid plasticizer, trimethylhydroquinone diacetate (melting point: 109 ° C.)
100 parts by weight, 15 parts by weight of an anionic surfactant (polycarboxylic acid ammonium salt) as a dispersant and 80 parts by weight of water were mixed, and the average particle diameter was 2.2 using a ball mill.
By pulverizing to a size of μm, an aqueous dispersion of trimethylhydroquinone diacetate (solid plasticizer aqueous dispersion 2) was obtained.

Preparation Example 3 (Preparation of aqueous dispersion of solid plasticizer 3) 100 parts by weight of dicyclohexyl phthalate (melting point: 65 ° C.) as a solid plasticizer and 15 parts by weight of an anionic surfactant (ammonium polycarboxylate) as a dispersant And 80 parts by weight of water, and pulverized using a ball mill until the average particle diameter becomes 2.2 μm, to obtain an aqueous dispersion of dicyclohexyl phthalate (aqueous dispersion of solid plasticizer 3).

Example 1 (Preparation of Thermosensitive Adhesive) Resorcinol bis [di (2,6-dimethylphenyl) phosphate] was prepared by mixing the aqueous dispersions of solid plasticizers 1 and 2 prepared above in a solid content ratio by weight. : Trimethylhydroquinone diacetate = 50:50 in an aqueous dispersion of a solid plasticizer, an acrylic polymer (2-ethylhexyl acrylate-styrene-acrylic acid copolymer as a thermoplastic resin, glass transition temperature) (Tg: 25 ° C.), an aqueous dispersion of a terpene resin as a tackifier and water were added, and the mixture was stirred until it became uniform to obtain a heat-sensitive adhesive having a solid content of 50% by weight. The mixing ratio at this time was 17 parts by weight of the thermoplastic resin (acrylic polymer) and 26 parts by weight of the tackifier (terpene resin) based on 100 parts by weight of the solid plasticizer. (Preparation of Heat-Sensitive Adhesive Sheet) A polyethylene terephthalate film (hereinafter referred to as “the heat-sensitive adhesive sheet”) was prepared by subjecting the heat-sensitive adhesive prepared above to corona discharge treatment on the base paper surface (back surface) of a single art paper weighing 84.9 g / m ² and the surface having a thickness of 25 μm. , Simply "PET
The film was also coated with a bar coater so that the coating amount after drying was 12 g / m ^2, and dried at 40 ° C. for 2 minutes to obtain a heat-sensitive adhesive sheet.

Example 2 (Preparation of Thermosensitive Adhesive) Resorcinol bis [di (2,6-dimethylphenyl) phosphate] was prepared by mixing the solid plasticizer aqueous dispersions 1 to 3 prepared above in terms of solid content weight ratio: An acrylic polymer (2-ethylhexyl acrylate-styrene-acrylic acid copolymer) as a thermoplastic resin was added to an aqueous dispersion of a solid plasticizer blended so that trimethylhydroquinone diacetate: dicyclohexyl phthalate = 45: 45: 10. , Glass transition temperature Tg: 25
° C), an aqueous dispersion of a terpene resin as a tackifier and water were added, and the mixture was stirred until it became uniform to obtain a heat-sensitive adhesive having a solid content of 48% by weight. The mixing ratio at this time was 17 parts by weight of the thermoplastic resin (acrylic polymer) and 26 parts by weight of the tackifier (terpene resin) based on 100 parts by weight of the solid plasticizer. (Preparation of heat-sensitive adhesive sheet) The heat-sensitive adhesive prepared above was weighed 84.9 g / m ² , and the corona discharge treatment was applied to the base paper surface (back surface) of a single art paper and the surface having a thickness of 25 μm.
The T film was coated using a bar coater so that the coating amount after drying was 12 g / m ^2, and dried at 40 ° C. for 2 minutes to obtain a heat-sensitive adhesive sheet.

Comparative Example 1 (Preparation of Thermosensitive Adhesive) An acrylic polymer (2-ethylhexyl acrylate) as a thermoplastic resin was added to the aqueous dispersion of dicyclohexyl phthalate (solid aqueous dispersion of plasticizer 3) prepared above. A water-based emulsion having a styrene-acrylic acid copolymer, a glass transition temperature Tg: 25 ° C.), a water-based dispersion of a terpene resin as a tackifier and water were added, and the mixture was stirred until uniform, and the solid content concentration was 50% by weight. Was obtained. The mixing ratio at this time was 17 parts by weight of the thermoplastic resin (acrylic polymer) and 26 parts by weight of the tackifier (terpene resin) based on 100 parts by weight of the solid plasticizer (dicyclohexyl phthalate). (Preparation of heat-sensitive adhesive sheet) The heat-sensitive adhesive prepared above was weighed 84.9 g / m ² , and the corona discharge treatment was applied to the base paper surface (back surface) of a single art paper and the surface having a thickness of 25 μm.
The T film was coated using a bar coater so that the coating amount after drying was 12 g / m ^2, and dried at 40 ° C. for 2 minutes to obtain a heat-sensitive adhesive sheet.

Performance Test (Adhesive Strength, Transparency) A heat-sensitive adhesive sheet obtained by coating a PET film was cut into a size of 25 mm in width and 125 mm in length to obtain a test piece. The test piece was heated at 140 ° C. for 30 seconds to develop adhesiveness, placed on a glass plate (Micro S1ide G1ass, white-green polishing, manufactured by Iwaki Glass Co., Ltd.), and reciprocated once with a rubber roll under a load of 2 kg. It was affixed. This was left in an atmosphere of 23 ° C. and 50% RH, and one day, one month, and three months later, an adhesive strength test was performed. In the adhesive strength test, the adhesive force was measured at a tensile speed of 300 mm / min and a peel angle of 180 ° using a tensile tester (Tensilon UCT-5T, manufactured by Orientec). Further, the transparency was visually confirmed. Table 1 shows the results. (Blocking resistance) Four heat-sensitive adhesive sheets obtained by coating on one side art paper are overlapped so that the glossy side (front side) of the art paper and the side (back side) coated with the heat-sensitive adhesive are in contact with each other. ,
After leaving to stand in a 40 ° C. atmosphere for 24 hours under a load of 500 gf / cm ² , the anti-blocking property was evaluated according to the following criteria. Table 1 shows the results. 5: Peeled without peeling resistance. 4: Peeling was performed with a slight sound when peeling. 3: Peeling was performed while making continuous sound during peeling. 2: Some paper fibers remained in the adhesive layer at the time of peeling. 1: The paper was torn by blocking.

[0079]

[Table 1] From the results in Table 1, the heat-sensitive adhesive sheet of Comparative Example 1 became opaque due to recrystallization of the solid plasticizer after one month, and the adhesive strength became 0. It can be seen that the adhesive sheet maintains high transparency and adhesive strength even after 3 months, and has excellent blocking resistance.

[0080]

According to the thermoplastic resin composition of the present invention, since two or more specific solid plasticizers are used in combination, not only the temperature at which tackiness is exhibited but also the recrystallization of the solid plasticizer is delayed. In addition, excellent transparency and adhesive strength are maintained for a long time. Therefore, the heat-sensitive adhesive sheet obtained by using the heat-sensitive adhesive sheet can be dried by heating at a higher temperature, does not cause blocking even when stored for a long time, and can maintain high transparency and adhesive strength for a long time.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (reference) C09J 7/02 C09J 7/02 Z 11/06 11/06 201/00 201/00 F-term (reference) 4J002 AB031 AC011 AC031 AC061 AC071 AC081 AE042 BB041 BB071 BB081 BB241 BC071 BD051 BF021 BG041 BG051 BJ001 CK021 EE056 EH136 EH146 EJ016 EJ066 ET016 EV286 EW016 EW046 EW066 FD022 FD026 FD200 FD340 GT00 4J004 AA04 AA05 AA06 AA07 AA09 AA10 AA14 AA17 AB01 AB03 CA02 CA04 CA05 CA06 CA08 CB01 CB02 CC02 DB01 FA01 GA01 4J040 CA011 CA131 DE021 DF041 DF051 HB32 HB34 HD22 HD24 JA03 JA09 JB09 JB11 KA31 LA10 LA11

Claims (10)

[Claims] 1. A thermoplastic resin composition comprising a thermoplastic resin and a solid plasticizer, wherein the solid plasticizer comprises (i-
1) a phosphorus compound having a melting point of 55 to 100 ° C, and (ii) (ii-
1) A thermoplastic resin composition comprising: a dioxybenzene derivative; and (ii-2) at least one compound selected from dicyclohexyl phthalate. 2. The phosphorus compound (i-1) is represented by the following formula (1) or (2): (Wherein, R ^{1 to} R ⁷ each represent a hydrocarbon group or a heterocyclic group, A represents a divalent hydrocarbon group or a heterocyclic group,
k represents 0 or 1, and m represents an integer of 0 to 3. R ¹ , R ² and A (when m = 1 to 3), R ³ , R ⁴ and A (m = 1
, R ¹ , R ^3, and R ⁴ (when m = 0), R ⁵ , R ^6, and R ⁷ form a ring containing a phosphorus atom by bonding of two or more groups to each other. The thermoplastic resin composition according to claim 1, which is a compound represented by the formula: 3. A thermoplastic resin composition containing a thermoplastic resin and a solid plasticizer, wherein the solid plasticizer comprises (i-
2) The following formula (1a), (1b), (1c) or (2) (Wherein, R ¹ , R ² , R ³ , R ⁴ , R ^1a , R ^3a , R ^4a ,
R ⁵ , R ⁶ and R ⁷ each represent a hydrocarbon group or a heterocyclic group; A represents a divalent hydrocarbon group or a heterocyclic group;
Represents 0 or 1, and n represents an integer of 1 to 3. Where R
^1a , R ^3a and R ^4a are not simultaneously a phenyl group or a 4-t-butylphenyl group. R ¹ and R ² and A, R ³ and R ⁴ and A, R ¹ and R ³ R ^1a and R ^3a and R ^4a in the formula (1b), in the formula (1c) and R ⁴ in Formula (1a), formula R ⁵ , R ^6, and R ⁷ in (2) may be a compound in which two or more groups may be bonded to each other to form a ring containing a phosphorus atom), and (ii) (ii- 1) A thermoplastic resin composition comprising: a dioxybenzene derivative; and (ii-2) at least one compound selected from dicyclohexyl phthalate. 4. The dioxybenzene derivative (ii-1)
(A) a diester compound of (A1) hydroquinone or resorcinol whose benzene ring may be substituted with an alkyl group, or (A2) catechol having a benzene ring substituted with an alkyl group, and (B) an organic monobasic acid. The thermoplastic resin composition according to claim 1 or 3. 5. The solid plasticizer content of the thermoplastic resin 10
2. The composition according to claim 1, wherein the amount is from 30 to 1,000 parts by weight per 0 parts by weight.
The thermoplastic resin composition according to the above. 6. The composition according to claim 1, further comprising a tackifier.
Item 5. The thermoplastic resin composition according to any one of Items 5. 7. The thermoplastic resin composition according to claim 1, wherein the thermoplastic resin is an aqueous composition dispersed in water. 8. A heat-sensitive adhesive containing the thermoplastic resin composition according to claim 1. 9. A heat-sensitive adhesive sheet having a pressure-sensitive adhesive layer comprising the heat-sensitive adhesive according to claim 8 on at least one surface of a substrate. 10. The method according to claim 8, wherein at least one surface of the substrate is provided.
A method for producing a heat-sensitive pressure-sensitive adhesive sheet, comprising applying the heat-sensitive pressure-sensitive adhesive described in the above and providing a pressure-sensitive adhesive layer.