JP2000212527A - Shrink label - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a shrink label capable of being firmly attached to a container, etc., in a simple way, and capable of maintaining excellent adhesiveness and transparency for a long period, by forming a specified delayed tack layer. SOLUTION: This shrink label is obtained by forming a delayed tack layer comprising a thermoplastic resin, a solid plasticizer and an adhesiveness- imparting agent on a shrink film, wherein the solid plasticizer comprises a combination of compounds of which the each compound is separately contained in different two or more groups selected from the following four groups of compounds: (i) a polyester compound of a polybasic acid and an alcohol having one or more alkyl-substituted cyclohexane rings or the like, (ii) a phosphorous compound having a melting point of 55-100 deg.C or a phosphorous compound expressed by formula I, II, III or IV [R1, R2, R3, R4, R1a, R3a, R4a, R5, R6, and R7 are each a hydrocarbon radical or a heterocyclic radical; A is a divalent hydrocarbon radical or a heterocyclic radical; (k) is 0 or 1; (n) is 1-3], (iii) a diester of a hydroquinone or resorcinol compound which may have an alkyl- substituted benzene ring, or of a catechol compound which has an alkyl- substituted benzene ring, and an organic monobasic acid, and (iv) dicyclohexyl phthalate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a shrink label for tightly covering containers by heat shrinkage.

[0002]

2. Description of the Related Art An adhesive layer is provided on a heat-shrinkable film as a label to be attached to containers such as bottles, PET bottles and cans, and is firmly fixed to an adherend by the adhesive and the heat shrinkage of the film. Shrink labels have been developed. For example, JP-A-62-227182 discloses a shrink label for a printed container in which a concealing layer and an adhesive layer containing a polyamide resin as a main component are sequentially formed on a shrink film. Also, Japanese Patent Application Laid-Open No. 4-31143
No. 2 has heat shrinkability in at least one direction,
A shrink label for a bottle is disclosed in which a film in which a pattern ink layer, an anchor resin layer, a metal deposition layer, and a heat-sensitive adhesive layer are sequentially laminated on one surface thereof is formed into a cylindrical shape. However, the labels described in these publications require a high temperature of about 180 to 280 ° C. to exhibit adhesiveness.

On the other hand, as a label that can be attached to an adherend at a relatively low temperature, a label called a delayed tack label is known. The delayed tack label is a non-adhesive at room temperature, but a layer of a heat-sensitive adhesive (delay tack layer) that develops tackiness upon heating is formed on a label base material, and no release paper is required. It has an advantage that it can be easily attached to a container only by heating to a relatively low temperature. The heat-sensitive adhesive is usually a mixture of a thermoplastic resin having a glass transition temperature of about 0 to 30 ° C., a solid plasticizer and, if necessary, a tackifier. It melts, and thereby plasticizes the thermoplastic resin to exhibit adhesiveness. As the solid plasticizer, for example, dicyclohexyl phthalate is well known (JP-A-61-9).
479, JP-A-7-278521, JP-A-7-145352, JP-A-8-333565, etc.).

If the adhesive layer of the shrink label is formed of such a delayed tack layer, it can be firmly attached to a container or the like at a relatively low temperature. However, when conventional dicyclohexyl phthalate or the like is used as a solid plasticizer to be contained in the delayed tack layer, the label can be once adhered to a container or the like, but the adhesive strength is reduced within a short period of time and the label is adhered to. There is a problem that a gap is formed between the body and the label, the label is easily dropped, and the transparency is reduced, so that the printed portion is difficult to see and the appearance is poor.

[0005]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to provide a shrink label which can be firmly fixed to a container or the like by a simple means and can maintain high adhesiveness and transparency for a long period of time.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to achieve the above object, and as a result, have found that the adhesive layer of a shrink label is composed of a delayed tack layer containing two or more specific solid plasticizers. The present inventors have found that not only can they be easily adhered and fixed to the like, but also can maintain high adhesiveness and transparency for a long period of time, and have completed the present invention.

That is, the present invention provides a shrink label comprising a shrink film and a delayed tack layer formed of a thermoplastic resin, a solid plasticizer and a tackifier, wherein the solid plasticizer comprises (i) ( A) (A1) an alcohol having a substituted cyclohexane ring or a substituted cyclohexene ring substituted with one or more alkyl groups and having a total number of carbon atoms of 3 or more, or (A2) a crosslink containing at least a 6-membered carbon ring A polyester compound of an alcohol having a ring and (B) a polybasic acid, (ii) a melting point of 55
To 100 ° C. phosphorus compound, or the following formula (1a), (1b),
(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), (iii) (C) (C1) a diester compound of hydroquinone or resorcinol whose benzene ring may be substituted with an alkyl group or (C2) a catechol having a benzene ring substituted with an alkyl group and (D) an organic monobasic acid, and (iv) dicyclohexyl Provided is a shrink label comprising a combination of compounds included in at least two compound groups among four compound groups of phthalate.

[0008]

Embodiments of the present invention will be described below. In the shrink label of the present invention, a delayed tack layer made of a thermoplastic resin, a solid plasticizer and a tackifier is formed on the shrink film.

[Thermoplastic Resin] The thermoplastic resin includes, for example, a homo- or copolymer of (meth) acrylate, a styrene- (meth) acrylate copolymer, and vinyl acetate- (meth) acrylic acid. Ester 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, vinylpyrrolidone- (meth) Acrylic ester copolymer, styrene-butadiene- (meth)
Acrylic polymer containing (meth) acrylic acid or its ester as a monomer such as acrylic acid copolymer; vinyl acetate resin containing vinyl acetate as a monomer such as vinyl acetate resin and ethylene-vinyl acetate copolymer Polymer: styrene-butadiene copolymer, isobutylene resin, isobutylene-isoprene copolymer, butadiene resin, styrene-
Synthetic rubber such as isoprene copolymer and acrylonitrile-butadiene copolymer; natural rubber; ethylene-vinyl chloride copolymer, vinyl chloride-vinylidene chloride copolymer, vinyl virolidone-styrene copolymer, chlorinated propylene resin, urethane resin , Ethyl cellulose and the like. These thermoplastic resins may be used alone or in combination of two or more.

Preferred thermoplastic resins include acrylic polymers [for example, 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 as long as the adhesiveness and the blocking resistance in the case of a shrink label are not impaired, 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.

[Solid Plasticizer] The main features of the present invention are as follows: (i) a polyester compound (first compound group); (ii) a phosphorus compound (second compound group);
(Iii) diester compounds (third compound group) and (i)
v) The point is that compounds included in at least two of the four compound groups of dicyclohexyl phthalate (fourth compound group) are used in combination.

[(I) Polyester compound] In the alcohol (A1) constituting the polyester compound (i),
Examples of the alkyl group that is a substituent of the cyclohexane ring or the cyclohexene ring include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, and hexyl groups. Preferred alkyl groups include alkyl groups having about 1 to 6 carbon atoms (particularly, 1 to 4 carbon atoms) such as methyl, isopropyl and t-butyl groups.

Examples of the alcohol having a substituted cyclohexane ring or a substituted cyclohexene ring (A1) substituted with one or more alkyl groups and having a total number of carbon atoms of 3 or more include the following formulas (I) to (I). (VI
Substituted cyclohexanols represented by I), (VIII) to
A substituted cyclohexenol represented by (X), (XI) to
Examples include a substituted cyclohexanol having a carbonyl group represented by (XII), a substituted cyclohexenol having a carbonyl group represented by (XIII), and the like. Also, (A
2) As the alcohol having a bridged ring containing at least a 6-membered carbon ring, for example, an alkylene group is bonded between two carbon atoms other than adjacent carbon atoms among the carbon atoms constituting the 6-membered carbon ring. Alcohols having a bridged ring forming a bridge, such as (XIV), (XV), (XVI),
Alcohols having a norbornane ring represented by (XVIII), alcohols having a norbornene ring represented by (XVII) and (XIX), alcohols having an adamantane ring represented by (XX) and (XXI), and the like. .

[0015]

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Embedded image Among these alcohols, (A11) such as alcohols represented by formulas (I) to (VII), substituted cyclohexanol substituted with one or more alkyl groups and having a total of 3 or more carbon atoms of a substituent; (A21) Alcohols having a bridged ring containing at least a 6-membered saturated carbon ring bonded to a hydroxyl group or a hydroxymethyl group, such as alcohols having a norbornane ring represented by formulas (XVI) and (XVIII), are preferred. In particular, 3,3,5-trimethylcyclohexanol represented by the formula (I) is preferable from the viewpoint of the temperature at which tackiness is exhibited and the blocking resistance.

The polybasic acid (B) includes polycarboxylic acids, polysulfonic acids, polyphosphonic acids and the like.
As the polyvalent carboxylic acid, the following formula

Embedded image

Embedded image (Phthalic anhydride, pyromellitic anhydride, cyclohexene-4,5-dicarboxylic anhydride, trimellitic anhydride) and the corresponding polyhydric carboxylic acids (phthalic acid, pyromellitic acid, cyclohexene-) 4,5-dicarboxylic acid, trimellitic acid) or the following formula

Embedded image And the like. Polycarboxylic acids (terephthalic acid, isophthalic acid) and the like can be exemplified. In the above formula, the benzene ring includes an alkyl group (eg, a C _1-4 alkyl group) such as a methyl, ethyl, isopropyl, or t-butyl group; an aryl group such as a phenyl or naphthyl group; an alkoxy group such as a methoxy or ethoxy group. Groups (for example, C _1-4 alkoxy groups); substituents such as halogen atoms such as fluorine, chlorine and bromine atoms may be substituted.

Among the polyester compounds (i) obtained from the above-mentioned (A) alcohol and (B) polybasic acid, from the viewpoint of the temperature at which plasticization starts to occur and the performance of tackiness upon heating, the formula (I) The following formula obtained by the reaction of 3,3,5-trimethylcyclohexanol represented by) with phthalic anhydride

Embedded image The bis (3,3,5-trimethylcyclohexyl) phthalate represented by is particularly preferable.

The 3,3,5-trimethylcyclohexanol has two geometric isomers, cis and trans, due to the steric positional relationship between the hydroxyl group and the methyl group at the 5-position. In the present invention, a polyester compound obtained from any isomer can be used.
Further, a polyester compound obtained from a mixture of these isomers can also be used.

The above-mentioned polyester compound (i) can be prepared from (A) alcohol and (B) polybasic acid or a reactive derivative thereof (for example, acid anhydride, acid halide, active ester, etc.)
It can be produced according to a known or common esterification method. For example, (A) alcohol and (B) a polybasic acid are reacted in a solvent such as toluene in the presence of a protonic acid catalyst, and water produced as a by-product is removed to remove the polyester compound (i). Can be obtained.

The melting point of the polyester compound (i) is preferably about 70 to 160 ° C. If the melting point of the polyester compound is lower than 70 ° C., the blocking resistance tends to decrease. If the melting point exceeds 160 ° C., it takes a long time to melt, and the productivity may decrease or the base material may be deteriorated. is there. The polyester compound (i) can be used alone or in combination of two or more.

[(Ii) Phosphorus compound] The phosphorus compound (i
i) includes phosphates, phosphites, phosphines and the like. As the phosphorus compound having a melting point of 55 to 100 ° C., 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; a 2-thienyl group And nitrogen-containing heterocyclic groups such as 1-pyrrolyl, 2-pyridyl, piperidino and 2-quinolyl groups. 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 A are 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, 1,1
-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 includes a divalent heterocyclic alcohol or phenol (for example, a saccharide such as isosorbide, isomannide, sucrose, lactose) from which two hydroxyl groups have been 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.

[0032] 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-cyclohexanedimethanolbis (diphenylphosphate) (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.

As a specific example of the compound (phosphate ester) represented by the formula (1b), 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 compound (ii) can be used alone or in combination of two or more.

[(Iii) Diester compound] In the diester compound (iii), the alkyl group as a substituent on the benzene ring of hydroquinone, resorcinol or catechol may be methyl, ethyl, propyl, isopropyl, butyl, isobutyl or s-butyl. 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 (C), 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 hydroquinone or resorcinol (C1) in which the benzene ring may be substituted with an alkyl group include hydroquinone, methylhydroquinone, 2,3-dimethylhydroquinone, 2,5-dimethylhydroquinone, and 2,6- 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 the catechol in which the (C2) benzene ring is substituted with an alkyl group include 3-methylcatechol, 4-methylcatechol, and trimethylcatechol.

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

As the aliphatic monocarboxylic acid, for example, 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 (preferably) 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 (C) with the component (D) 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-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, the acid catalyst may be 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 melting point of the diester compound (iii) may be, for example, about 50 to 160 ° C., preferably 9
It is about 0 to 130 ° C. If the melting point of the diester compound (iii) 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 the productivity may decrease or the base material may be deteriorated. The diester compound (iii) can be used alone or in combination of two or more.

In the present invention, as the solid plasticizer, compounds included in at least two of the four compound groups (i) to (iv) are used in combination. As the embodiment, (1) a combination of the polyester compound (i) and the phosphorus compound (ii), (2) a combination of the polyester compound (i) and the diester compound (iii),
(3) Combination of polyester compound (i) and dicyclohexyl phthalate (iv), (4) phosphorus compound (ii)
(5) a combination of phosphorus compound (ii) and dicyclohexyl phthalate (iv), (6) a combination of diester compound (iii) and dicyclohexyl phthalate (iv), (7)
(8) Combination of polyester compound (i), phosphorus compound (ii) and diester compound (iii), (8) combination of polyester compound (i), diester compound (iii) and dicyclohexyl phthalate (iv), (9) Combination of phosphorus compound (ii), diester compound (iii) and dicyclohexyl phthalate (iv), and (10) combination of polyester compound (i), phosphorus compound (ii), diester compound (iii) and dicyclohexyl phthalate (iv) Combinations are included. Among these, a combination including compounds included in at least two of the three compound groups of the polyester compound (i), the phosphorus compound (ii), and the diester compound (iii) is preferable.

At least two of the above four compound groups
Each of the compounds contained in the compound group is, for example, about 1 to 99% by weight, particularly 5 to 99% by weight, based on the total amount of the solid plasticizer.
It is preferably about 95% by weight, especially about 5 to 80% by weight.

In the present invention, the content of the solid plasticizer in the delayed tack layer is, for example, 30 to 1000 parts by weight, preferably 1 to 100 parts by weight of the thermoplastic resin.
00 to 1000 parts by weight, more preferably 150 to 90 parts by weight
0 parts by weight, particularly about 200 to 800 parts. 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.

In the shrink label of the present invention, a plurality of different kinds of compounds belonging to a specific compound group are used in combination as the solid plasticizer to be contained in the delayed tack layer as described above. In addition to being plasticized, recrystallization of the solid plasticizer is delayed, and high transparency and adhesion are maintained for a long time. Therefore, it can be firmly fixed to a container such as a bottle for a long period of 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; triphenyl phosphate, tri (phosphate)
-Butylphenyl) and other phosphorus compounds; sucrose benzoate, ethylene glycol dibenzoate, trimethylolethane tribenzoate, glyceryl tribenzoate,
Pentaerythroate tetrabenzoate, sucrose octaacetate, tricyclohexyl citrate, N-cyclohexyl-p-
Examples include toluenesulfonamide, urea derivatives, and paraffin chloride.

[Tackifiers] The tackifiers constituting the delayed tack layer include, for example, terpene resins,
Aliphatic petroleum resin, aromatic petroleum resin, cumarone-indene resin, styrene resin, phenol resin, terpene-phenol resin, rosin derivative (rosin, polymerized rosin, hydrogenated rosin and their glycerin, pentaerythritol, etc. Esters, resin acid dimers, etc.) and xylene resins. Two or more of these tackifiers may be used in combination.

Although the content of the tackifier in the delayed tack layer is not particularly limited, it can be appropriately selected according to the combination of the thermoplastic resin and the solid plasticizer.
About 10 to 600 parts by weight, preferably about 20 to 500 parts by weight, based on 100 parts by weight of the thermoplastic resin.

In the delayed tack layer, conventional additives such as antifoaming agents, coating improvers, thickeners, lubricants and stabilizers (antioxidants, ultraviolet absorbers, Heat stabilizers, etc.), antistatic agents, and antiblocking agents (inorganic particles, organic particles, etc.) may be added.

[Delayed Tack Layer] The delayed tack layer can be formed by applying a thermoplastic resin composition containing the thermoplastic resin, a solid plasticizer and a tackifier on a shrink film. For example, an aqueous composition in which the thermoplastic resin is dispersed in water is applied, or the thermoplastic resin or the like is dissolved in an organic solvent and applied, or the thermoplastic resin composition is heated and melted. The coating can form a delayed tack layer. Among these, a method of applying an aqueous composition in which a thermoplastic resin is dispersed in water is preferred.

In the aqueous composition, the dispersant used for dispersing the thermoplastic resin is not particularly limited, and any of conventionally known anionic and nonionic dispersants can be used. it can. 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 are mixed in advance and then dispersed in water, and these emulsions are dispersed after dispersing the solid plasticizer in the thermoplastic resin emulsion or the tackifier emulsion. A mixing method, a method in which a solid plasticizer is dispersed in water, and a method in which a thermoplastic resin emulsion and a tackifier emulsion are mixed with the dispersion, and the like, may be used. 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, 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 coating method of the thermoplastic resin composition includes:
For example, 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, or the like can be used. The thickness of the delayed tack layer is, for example, 4 to 20 μm, preferably 5 to 15 μm.
It is about μm.

[Shrink Label] In the shrink label of the present invention, a conventionally known heat-shrinkable plastic film exhibiting heat shrinkage in at least one direction can be used as a shrink film as a base material. For example, polyvinyl chloride; Polyolefins such as polyethylene and polypropylene; styrene resins such as polystyrene; polyesters such as polyethylene terephthalate; uniaxially or biaxially stretched films composed of composites of these. The thickness of the shrink film is, for example, 15 to 15
0 μm, preferably about 20 to 120 μm.

At least one surface of the shrink film may be provided with a printed layer for forming characters, patterns, and the like. The printing layer can be formed by printing on a shrink film by a conventional printing method (for example, letterpress printing, flat plate printing, gravure printing, etc.).

Further, a hiding layer may be formed between the shrink film and the delayed tack layer. When the shrink label having the concealing layer is applied to a printed container or the like, an unnecessary display directly printed on the container or the like can be prevented from visually touching. The concealing layer is
It can be formed by printing or applying a composition containing a substance having a hiding power using a conventional printing method or coating method. For example, the substance having a hiding power, a vehicle (oil, resin, solvent, plasticizer, etc.), an additive (wax,
A concealing layer can be formed by printing a printing ink comprising a surfactant or the like by a conventional printing method.

Examples of substances having a hiding power include white pigments such as titanium oxide and zinc oxide, black pigments such as carbon black, pigments such as blue pigments, and metal powders such as aluminum powder and bronze powder. The resin constituting the vehicle is not particularly limited and includes, for example, natural resins (rosin, shellac, gilsonite, etc.), natural resin derivatives (rosin derivatives, etc.), synthetic resins (phenol resins, ketone resins, polyvinyl chloride, chlorine, etc.). Polypropylene, acrylic resin, polyester resin, polyamide resin, cellulose derivative, etc.). In order to prevent the concealment layer from peeling off from the delayed tack layer, it has an affinity for the thermoplastic resin constituting the delayed tack layer. It is preferable to use a resin having properties. The concealing layer may be composed of a plurality of layers. When a printing layer is formed on the surface of the shrink film on the side of the delayed tack layer, the concealing layer is formed between the printing layer and the delayed tack layer. The thickness of the concealing layer is, for example, 3 to
It is about 20 μm, preferably about 4 to 15 μm.

Further, in order to obtain a metallic luster, a metal deposition layer may be provided between the shrink film and the delayed tack layer. When a printing layer is formed on the surface of the shrink film on the side of the delayed tack layer, the metal deposition layer is formed between the printing layer and the delayed tack layer. Examples of the metal constituting the metal deposition layer include aluminum, chromium, nickel, and the like. The deposition layer can be formed by a conventional method, for example, a vacuum deposition method, an ion plating method, a sputtering method, or the like. The thickness of the metal deposition layer is, for example, 0.01 to 0.5 μm, preferably 0.02 to 0.3 μm.
It is about μm.

The shrink label of the present invention may be used in a flat shape, but is often used in a cylindrical shape with a delayed tack layer inside. The shrink label of the present invention can be used for, for example, plastic containers such as so-called PET bottles, glass containers, metal containers, and the like.

[0077]

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 bis (3,3,5-trimethylcyclohexyl) phthalate (melting point: 93 ° C.) as a solid plasticizer and anionic surfactant as a dispersant By mixing 15 parts by weight of an agent (ammonium polycarboxylate) and 80 parts by weight of water and pulverizing with a ball mill until the average particle size becomes 2.2 μm,
An aqueous dispersion of bis (3,3,5-trimethylcyclohexyl) phthalate (solid plasticizer aqueous dispersion 1) was obtained.

Preparation Example 2 (Preparation of aqueous dispersion of solid plasticizer 2) 100 parts by weight of resorcinol bis [di (2,6-dimethylphenyl) phosphate] (melting point: 95 ° C.) as a solid plasticizer and an anionic dispersion as a 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 2).

Preparation Example 3 (Preparation of aqueous dispersion of solid plasticizer 3) Trimethylhydroquinone diacetate (melting point: 109 ° C.) as a solid plasticizer
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 3) was obtained.

Preparation Example 4 (Preparation of solid plasticizer aqueous dispersion 4) 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 4).

Example 1 The solid plasticizer aqueous dispersions 1 and 2 prepared above were mixed with bis (3,3,5-trimethylcyclohexyl) phthalate: resorcinol bis [di (2,6- [Dimethylphenyl) phosphate] = 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 are added, and the mixture is stirred until uniform, and a heat-sensitive adhesive (solid content: 47% by weight) (thermoplastic resin composition) I got At this time, the mixing ratio was such that 17 parts by weight of the thermoplastic resin (acrylic polymer) and 26 parts by weight of the tackifier (terpene resin) were added to 100 parts by weight of the solid plasticizer.
Parts by weight. Apply the heat-sensitive adhesive prepared above to a thickness of 2
A coating amount after drying with a bar coater on one side of a 5 μm polyvinyl chloride shrink film is 10 g / m 2.
^The coating was performed so as to be ² and dried at 40 ° C. for 2 minutes. The film was cut into a width of 7 cm and a length of 29 cm, formed into a tubular shape with the pressure-sensitive adhesive layer inside, and bonded at both ends with an adhesive to produce a shrink label. A position is determined outside the polyethylene terephthalate bottle (hereinafter, also simply referred to as a “PET bottle”), and the shrink label is temporarily fixed.
When placed in an oven at a temperature of 3 ° C. for 3 minutes, the label was fixed at a desired position by the shrinkage of the shrink label and the adhesive force of the heat-sensitive adhesive.

Example 2 The solid plasticizer aqueous dispersions 1 and 3 prepared above were mixed with bis (3,3,5-trimethylcyclohexyl) phthalate: trimethylhydroquinone diacetate = 50: 50 by solids weight ratio. In the aqueous dispersion of the solid plasticizer compounded as described above, an acrylic polymer (2-
An ethyl hexyl acrylate-styrene-acrylic acid copolymer, an aqueous emulsion having a 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 uniform, and the solid content concentration was 50%. By weight, a heat-sensitive adhesive (thermoplastic resin composition) 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. The above-prepared heat-sensitive adhesive was applied to the printed surface of a 30 μm-thick polyethylene shrink film having one side printed thereon, with a width of 1 mm.
Gravure coating was performed in the form of stripes at intervals and dried at 40 ° C. The film was cut into a width of 7 cm and a length of 29 cm, formed into a cylinder with the pressure-sensitive adhesive layer inside, and heat-sealed at both ends to produce a shrink label. Determine the position on the outside of the PET bottle and temporarily fix the shrink label.
When placed in the oven for 3 minutes, the label was fixed at a desired position by the shrinkage force of the shrink label and the adhesive force of the heat-sensitive adhesive.

Example 3 The solid plasticizer aqueous dispersions 1 to 3 prepared above were mixed with bis (3,3,5-trimethylcyclohexyl) phthalate: resorcinol bis [di (2,6-dimethyl) in terms of solids weight ratio. Phenyl) phosphate]: An acrylic polymer (2-ethylhexyl acrylate-) as a thermoplastic resin was added to an aqueous dispersion of a solid plasticizer mixed so that trimethylhydroquinone diacetate = 35: 35: 35.
Styrene-acrylic acid copolymer, glass transition temperature Tg:
(25 ° C.), an aqueous dispersion of a terpene resin as a tackifier and water are added, and the mixture is stirred until uniform, to obtain a heat-sensitive adhesive (thermoplastic resin composition) having a solid content of 48% by weight. Was. 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. On the side opposite to the printed side of a 30 μm thick polyethylene shrink film with one side printed,
The heat-sensitive adhesive prepared above was gravure-coated in halftone dots and dried at 40 ° C. 7cm width, 2 length film
It was cut into 9 cm, made cylindrical with the pressure-sensitive adhesive layer inside, and heat-sealed at both ends to produce a shrink label. PE
Place the shrink label temporarily on the outside of the T bottle and place it in a 120 ° C oven for 3 minutes.
The label was fixed at a desired position by the shrinking force of the shrink label and the adhesive force of the heat-sensitive adhesive.

Example 4 The solid plasticizer aqueous dispersions 1 to 4 prepared above were mixed with bis (3,3,5-trimethylcyclohexyl) phthalate: resorcinol bis [di (2,6-dimethyl) in a weight ratio of solid content. Phenyl) phosphate]: trimethylhydroquinone diacetate: dicyclohexyl phthalate = 3
An acrylic polymer (2-ethylhexyl acrylate-styrene-acrylic acid copolymer, as a thermoplastic resin, a glass transition temperature Tg :) in a solid plasticizer aqueous dispersion compounded so as to be 0: 30: 30: 10. (25 ° C.), an aqueous dispersion of a terpene resin as a tackifier and water are added, and the mixture is stirred until uniform, to obtain a heat-sensitive adhesive (thermoplastic resin composition) having a solid content concentration of 45% by weight. Was. 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. The above-prepared heat-sensitive adhesive was gravure-coated in a single area of 1 cm square in a range of 7 cm in width and 29 cm in length on a printing surface of a 25 μm-thick polyethylene terephthalate shrink film having one side printed thereon, Dry at ℃. The film was cut into a width of 7 cm and a length of 29 cm, formed into a cylinder with the pressure-sensitive adhesive layer inside, and heat-sealed at both ends to produce a shrink label. After positioning the shrink label temporarily on the outside of the PET bottle and placing it in an oven at 120 ° C for 3 minutes, the label is fixed at the desired position by the shrinkage of the shrink label and the adhesive force of the heat-sensitive adhesive. Was done.

Comparative Example 1 A polyvinyl chloride shrink film having a thickness of 25 μm was cut into a width of 7 cm and a length of 29 cm, formed into a cylinder, and both ends were adhered with an adhesive to produce a shrink label. PE
Place the shrink label temporarily on the outside of the T bottle and place it in a 100 ° C oven for 3 minutes.
The label was fixed at a desired position by the shrinking force of the shrink label.

Comparative Example 2 A 30 μm-thick polyethylene shrink film having one side printed was cut to a width of 7 cm and a length of 29 cm, and the printed surface was formed inside to form a cylinder, and both ends were heat-sealed to produce a shrink label. did. The shrink label was temporarily fixed at a position outside the PET bottle and placed in an oven at 120 ° C. for 3 minutes, and the label was fixed at a desired position by the shrinkage force of the shrink label.

Comparative Example 3 In the aqueous dispersion of dicyclohexyl phthalate prepared above (solid plasticizer aqueous dispersion 4), an acrylic polymer (2-ethylhexyl acrylate) as a thermoplastic resin was used.
Styrene-acrylic acid copolymer, 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 concentration of 50% by weight. At this time, the blending ratio was such that 17 parts by weight of the thermoplastic resin (acrylic polymer) and 2 parts of the tackifier (terpene resin) were added to 100 parts by weight of the solid plasticizer (dicyclohexyl phthalate).
6 parts by weight. The above-prepared heat-sensitive adhesive was coated on the printed surface of a 25 μm-thick polyvinyl chloride shrink film with one side printed thereon using a bar coater so that the coating amount after drying was 10 g / m ^2. Coated and dried at 40 ° C. for 2 minutes. 7cm width and 29cm length film
Into a cylindrical shape with the pressure-sensitive adhesive layer on the inside, and bonded at both ends with an adhesive to produce a shrink label. After positioning the shrink label temporarily on the outside of the PET bottle and placing it in an oven at 100 ° C for 3 minutes, the label is fixed at the desired position by the shrinkage of the shrink label and the adhesive force of the heat-sensitive adhesive. Was done.

Performance Test (Transparency) The PET bottle to which the shrink label was affixed was left in an atmosphere of 23 ° C. and 50% RH.
After three months, the transparency was visually confirmed after three months. Table 1 shows the results.

(Adhesion) The PET bottle to which the shrink label was attached was placed at -5 ° C. for 10 hours at 23 ° C., 5 ° C.
A cycle test in which the label is dropped for 10 hours under the condition of 0% RH, 10 hours under the condition of 40 ° C. and 80% RH, and 10 hours under the condition of 23 ° C. and 50% RH is repeated 10 times, and whether the label falls or not is repeated. Was checked, and when not dropped, it was evaluated as ○, and when it fell, it was evaluated as ×. Table 1 shows the results.

[0091]

[Table 1] As is clear from the results in Table 1, the labels of Comparative Examples 1 and 2 failed to follow the deformation due to the environmental change of the PET bottle and fell, and the label of Comparative Example 3 was recrystallized after 1 month because the solid plasticizer recrystallized. The printed portion became opaque and the printed portion became difficult to see, and the adhesive strength was reduced and the printed portion was dropped. On the other hand, the labels of Examples 1 to 4 maintained high transparency even after three months, did not decrease in adhesive strength, and did not drop.

[0092]

The shrink label of the present invention uses two or more compounds contained in a specific compound group as a solid plasticizer to be contained in the delayed tack layer. Recrystallization of the solid plasticizer is delayed, and excellent transparency and adhesive strength are maintained for a long time. Therefore, it can be firmly fixed to an adherend such as a container for a long period of time.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AH02B AH10B AK01B AK12 AK15 AK25 AL01 AR00C AT00A BA03 BA07 BA10A CA04B CA04H CA04K CA16B CA16H EH46 GB90 HB31 HB31A JA03A JB16B JL12 JLAJA A04A04 AA17 AB03 CA04 CA05 CA06 CC02 CC03 CC04 CD01 FA01 FA06 4J040 BA08 CA01 CA071 CA081 DA051 DA061 DA071 DA101 DA131 DA141 DA181 DB041 DB051 DB061 DC021 DE021 DE031 DF041 DF051 DF081 DH031 DN05 HD01 GA03 GA03 GA03B01 HD03 GA03 GA03 KA31 LA06 LA07 LA08 LA10 MA10 NA06

Claims (6)

[Claims] 1. A shrink label having a delayed tack layer formed of a thermoplastic resin, a solid plasticizer, and a tackifier on a shrink film, wherein the solid plasticizer comprises (i) (A) (A1 A) an alcohol having a substituted cyclohexane ring or a substituted cyclohexene ring substituted with one or more alkyl groups and having a total number of carbon atoms of 3 or more, or (A2) an alcohol having a bridged ring containing at least a 6-membered carbon ring And (B) a polyester compound with a polybasic acid, (ii) a phosphorus compound having a melting point of 55 to 100 ° C., or a compound represented by 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 two or more groups bonded to each other to form a ring containing a phosphorus atom), (iii) (C) (C1) hydroquinone or resorcinol in which the benzene ring may be substituted with an alkyl group or (C2) a diester compound of (C) a catechol in which the benzene ring is substituted with an alkyl group and (D) an organic monobasic acid, and (iv) dicyclohexyl A shrink label comprising a combination of compounds included in at least two of the four compound groups of phthalate. 2. The polyester compound (i) is (A11) 1
Or a substituted cyclohexanol substituted with a plurality of alkyl groups and having a total number of carbon atoms of 3 or more, or (A21) having a bridged ring containing at least a 6-membered saturated carbocycle bonded to a hydroxyl group or a hydroxymethyl group. The shrink label according to claim 1, which is a polyester compound of an alcohol and (B) a polybasic acid. 3. The content of the solid plasticizer in the delayed tack layer is 30 to 1 with respect to 100 parts by weight of the thermoplastic resin.
The shrink label according to claim 1 or 2, which is 000 parts by weight. 4. The delayed tack layer comprises a thermoplastic resin,
The shrink label according to any one of claims 1 to 3, comprising a solid plasticizer and a tackifier, and wherein the thermoplastic resin is formed by applying an aqueous composition dispersed in water. 5. The shrink label according to claim 1, wherein a print layer is provided on at least one surface of the shrink film. 6. The shrink label according to claim 1, wherein a hiding layer is provided between the shrink film and the delayed tack layer.