JPH09169870A - Crystallization retarder, thermoplastic resin composition, solid plasticizer composition, tacky adhesive, and tacky adhesive substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a crystallization retarder which is mixed into a solid plasticizer to improve the balance between the blocking resistance and adhesive properties of a heat-sensitive delayed-tack type tacky adhesive thermoplastic resin compsn. contg. the plasticizer by using a compd. having specified properties as the retarder. SOLUTION: This crystallization retarder for a solid plasticizer has such properties that when mixed in an amt. of 30wt.% into a solid plasticizer and melted, it increases the crystallization time of the plasticizer to at least twice. Pref. the retarder is a solid polyester formed by reacting a polyhydric alcohol, pref. an aliph. polyhydric alcohol or a polyhydric alcohol having a bisphenol backbone, with an arom. monobasic acid or by reacting an arom.-substd. alkyl alcohol, pref. benzyl alcohol, with a polybasic acid.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a heat-sensitive delayed-tack type thermoplastic resin composition using a specific crystallization retarder and a plasticizer, which is excellent in blocking resistance and adhesiveness, a pressure-sensitive adhesive, and a pressure-sensitive adhesive thereof. The present invention relates to a heat-sensitive delayed tack type pressure-sensitive adhesive base material obtained by coating on a base material. This heat-sensitive delayed tack type adhesive substrate is useful as a label for, for example, alcohol bottles, soft drink bottles, shampoo bottles, pharmaceutical bottles, motor oil cans, and stationery boxes.

[0002]

2. Description of the Related Art Conventional heat-sensitive delayed tack adhesives which are non-adhesive at room temperature but which appear to be sticky by heating, and which remain sticky for a long time after being released from the heat source As described in "Adhesion Handbook", 12th Edition (published by Kobunshi Kogyokai, 1980), a thermoplastic resin, a tackifier, and a solid plasticizer are used as a basic skeleton. The thermoplastic resin forms the basis of the pressure-sensitive adhesive, and cohesive force at the time of use cannot be obtained without it. Further, the solid plasticizer does not give plasticity to the resin at room temperature, but it is melted by heating and swells or dissolves the resin to develop tackiness. And once melted, it solidifies slowly, so
After heating, stickiness is maintained for a certain period of time. The tackifier is a component for increasing the tackiness when activated by heating. The form of the coating liquid for producing the heat-sensitive delayed tack type pressure-sensitive adhesive sheet is a hot melt type (eg, JP-A-55-16055 and JP-A-56-1).
No. 06984), organic solvent type (eg; JP-A-51)
No. 111246 gazette) and an aqueous type (“polymer latex adhesive” by Soichi Muroi, published by Polymer Publishing Association) are known.

However, when the pressure-sensitive adhesive sheet is rolled up and stored, it is difficult to peel off due to the slight adhesiveness of the pressure-sensitive adhesive contact surface, and some printers generate heat during label printing. However, there is a problem that the blocking resistance is poor, which means that the property is poor.

As a method of improving the blocking resistance, a method of adding a wax to the pressure-sensitive adhesive component is disclosed in JP-B-62-218.
However, it is not sufficient. Also,
Japanese Patent Laid-Open No. 172784/1988 discloses a method in which the smoothness of the coated surface is set within a certain numerical range when the adhesive is coated on the substrate, but it is difficult to control the smoothness of the coated surface. Is.

[0005]

DISCLOSURE OF THE INVENTION The present invention is directed to a crystallization retarder which improves the balance of blocking resistance and adhesiveness of a conventional thermosensitive delayed tack adhesive thermoplastic resin composition, and a thermoplastic resin containing the same. A composition, an adhesive comprising the same, and an adhesive substrate using the same.

[0006]

DISCLOSURE OF THE INVENTION The present inventors have found that a crystallization retarder and a plasticizer to be added to a heat-sensitive delayed tack type tacky thermoplastic resin composition having good blocking resistance without deteriorating adhesiveness. As a result of earnest research on the above, the present invention has been completed.

That is, the present invention relates to a crystallization retarder for a solid plasticizer having a property of doubling the crystallization time until re-crystallization when it is mixed and melted in a solid plasticizer in an amount of 30% by weight. And a crystallization retarder characterized by being a polyester compound consisting of a polyvalent alcohol and an aromatic monobasic acid or a polyester compound consisting of an aromatic group-substituted alkyl alcohol and a polybasic acid, (a) a thermoplastic resin, (b) a tackifier, (c) a solid plasticizer, and (d) a polyester compound consisting of a polyvalent alcohol and an aromatic monobasic acid or an aromatic group-substituted alkyl alcohol and a polybasic compound. A crystallization retarder which is a polyester compound consisting of an acid, preferably a thermoplastic resin composition comprising a solid crystallization retarder, preferably a thermoplastic resin (a), is an emulsion type thermoplastic resin, preferably Solid plasticity (c) a fine powder and a crystallization retarder (d) a solid plasticizer composition comprising a mixture of fine powder and a thermoplastic resin composition containing the same, a pressure-sensitive adhesive using the same and a pressure-sensitive adhesive thereof. The present invention provides a heat-sensitive delayed tack type adhesive substrate, preferably a label, which is applied to a substrate.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The crystallization retarder (d) of the present invention has a property of doubling the crystallization time until recrystallization when it is mixed with 30% by weight in a solid plasticizer and melted. Having, preferably a polyester compound consisting of a polyhydric alcohol (A) and an aromatic monobasic acid (B) or a polyester compound consisting of an aromatic group-substituted alkyl alcohol (C) and a polybasic acid (D) Is. A solid compound is preferable.

This crystallization time means that 2 g of a sample is heated and melt-mixed in a bis tube (10 ml) at a temperature 20 ° C. higher than the melting point of the sample and allowed to stand at room temperature for cooling, and after the start of cooling until the end of crystallization. The crystallization retarder of the present invention, the crystallization time of the solid plasticizer only,
It has the property of doubling the crystallization time of the solid plasticizer / crystallization retarder (= 70/30% by weight) mixture. It is preferably three times or more. The longer this crystallization time is, the longer the stickiness of the pressure-sensitive adhesive becomes, which is preferable.

As the polyhydric alcohol (A), ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3
-Butanediol, 2-methyl 1,3-propanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl 1,5-pentanediol, 1,6-hexanediol, 2 , 2,
4-trimethyl 1,3-pentanediol, 2-ethyl 1,3-hexanediol, 2-methyl 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,12-octadecanediol Aliphatic glycols such as, polyalkylene glycols such as diethylene glycol, dipropylene glycol, hydrogenated bisphenol A, bisphenol A or bisphenol S
Ethylene oxide adduct of 1,4-cyclohexanedimethanol, 1,4-cyclohexanediol, 1,
Alicyclic or aromatic ring-containing dihydric alcohol such as 2-cyclohexanediol, bishydroxyethoxybenzene, hydrogenated bisphenol A, ethylene oxide adduct of bisphenol A or bisphenol S, glycerin,
Trimethylol propane, ditrimethylol propane,
Examples thereof include aliphatic polyhydric alcohols such as pentaerythritol, dipentaerythritol, sorbitol and mannitol.

Examples of the aromatic monobasic acid (B) include alkylbenzoic acid such as benzoic acid, p-toluic acid, m-toluic acid, o-toluic acid, p-methoxybenzoic acid and pt-butylbenzoic acid. Examples thereof include aryl acetic acid such as acid, phenylacetic acid, diphenylacetic acid, p-tolylacetic acid, m-tolylacetic acid, and o-tolylacetic acid. Examples of the aromatic group-substituted alkyl alcohol (C) include benzyl alcohol, 2-phenylethanol, 1-phenylethanol, 2-phenoxyethanol, 3-phenyl-1-
Propanol, 2-hydroxyethyl benzyl ether and the like can be mentioned.

Examples of the polybasic acid (D) include saturated aliphatic dibasic acids having 2 to 12 carbon atoms such as oxalic acid, succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid and dodecanedicarboxylic acid, and phthalic acid. , Polyphthalic acid such as isophthalic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, α, β-bis (4-carboxyphenoxy) ethane, trimellitic acid and pyromellitic acid Acid, hexahydrophthalic acid, 1,4
-Cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, saturated alicyclic dibasic acid such as hexahydrophthalic anhydride and maleic acid, fumaric acid, itaconic acid, citraconic acid, glutaconic acid, mesaconic acid, β-hydromuconic acid, And unsaturated dibasic acids such as tetrahydrophthalic acid or their anhydrides.

As the polyester compound which is a crystallization retarder composed of an alcohol and an acid, the polyhydric alcohol is an aliphatic polyhydric alcohol or a compound having a bisphenol skeleton, and an aromatic group-substituted alkyl alcohol. , Preferably benzyl alcohol,
For example, ditrimethylolpropane tetrabenzoate,
Examples thereof include pentaerythritol tetrabenzoate, bisphenol A ethylene oxide adduct dibenzoate, and tribenzyl trimellitate. Of these, esters having a melting point of 75 ° C to 140 ° C are preferable. If the melting point is lower than 75 ° C, the blocking resistance is poor, and 1
If it exceeds 40 ° C, it takes time to heat the pressure-sensitive adhesive, productivity is deteriorated, and the substrate may be deteriorated.

The crystallization retarder (d) of the present invention improves the stickiness persistence of the thermoplastic resin composition by delaying the crystallization of the plasticizer, and provides the thermoplastic resin with blocking resistance and adhesiveness. A composition having an excellent balance of These crystallization retarders (d) can be used alone or in admixture of two or more. In addition, if necessary, another crystallization retarder may be used in combination within a range that does not impair the effects of the present invention.

The amount of the crystallization retardant (d) used in the present invention is preferably 5 to 250 parts by weight, more preferably 10 to 100 parts by weight, based on 100 parts by weight of the thermoplastic resin (a).

Examples of the solid plasticizer (c) of the present invention include diphenyl phthalate, dihexyl phthalate, dicyclohexyl phthalate, dimethyl phthalate, diphenoxyethyl isophthalate, tribenzyl trimellitate, sucrose benzoate and dibenzoic acid. Examples thereof include ethylene glycol, trimethylolethane tribenzoate, triglyceride tribenzoate, pentaerythritol tetrabenzoate, sucrose octaacetate, tricyclohexyl citrate, N-cyclohexyl-p-toluenesulfonamide, and the like, and solid ones thereof. Is preferred.

The amount of the solid plasticizer (c) used in the present invention is preferably 30 to 500 parts by weight, and particularly preferably 50 to 250 parts by weight, based on 100 parts by weight of the thermoplastic resin (a).

Solid plasticizer (c) and crystallization retarder (d) of the present invention
The solid plasticizer (c) is a polyester compound composed of an aromatic group-substituted alkyl alcohol and a polybasic acid, and the crystallization retardant (d) is a polyvalent alcohol and an aromatic monobasic compound. It is preferably a polyester compound composed of an acid.

The thermoplastic resin (a) of the present invention is preferably an emulsion type resin such as vinyl acetate type, acrylic type, styrene type resin and rubber type resin.
Specifically, for example, polyvinyl acetate, polybutyl methacrylate, vinyl chloride-vinylidene chloride copolymer, ethylene-vinyl chloride, ethylene-acrylic acid ester copolymer, vinyl acetate-2-ethylhexyl acrylate, vinyl acetate-ethylene copolymer, Ethylene-vinyl acetate-acrylic acid ester copolymer, vinylpyrrolidone-styrene copolymer, vinylpyrrolidone-ethyl acrylate copolymer, polybutadiene, styrene-butadiene copolymer, styrene-butadiene block copolymer, styrene-isoprene block copolymer,
Styrene-butadiene-methacrylic acid copolymer, styrene-butadiene-acrylic acid copolymer, styrene-
Examples thereof include acrylic acid ester copolymer, urethane resin, chlorinated polypropylene, ethyl cellulose and the like.
Two or more of these thermoplastic resins may be used in combination. Further, in terms of blocking resistance, the glass transition temperature is -5 ° C.
The above is preferred.

Examples of the tackifier (b) of the present invention include terpene resins (homopolymers such as α-pinene, β-pinene and dipentene or copolymers thereof, terpenes,
Terpene / phenol copolymers, hydrogenated products thereof, etc., aliphatic petroleum resins, aromatic petroleum resins, coumarone-indene resins, styrene resins, phenol resins,
Terpene-phenolic resin, rosin derivative (rosin such as rosin abietic acid, polymerized rosin, hydrogenated rosin,
And esters thereof with glycerin, pentaerythritol, ethylene glycol, diethylene glycol and the like, maleic acid adducts, resin acid dimers and the like). The softening point of the tackifier (b) is preferably 70 to 145 ° C. The amount of tackifier used is 100% of the thermoplastic resin (a).
Preferably 10 to 200 parts by weight, especially 4
0 to 150 parts by weight is preferred. When it is less than 10 parts by weight, the viscosity and adhesive strength of the thermoplastic resin (a) are low, and when it exceeds 200 parts by weight, the blocking resistance becomes poor.

In addition to the above, as additives, titanium oxide,
Inorganic substances such as alumina, colloidal silica, kaolin, and talc, organic substances such as paraffin, natural wax, natural resin, and powdered styrene, and, if necessary, a dispersant and a defoaming agent,
Thickeners and the like can also be used. When a solid plasticizer is used, it may be coated with an inorganic compound such as titanium oxide, magnesium oxide or aluminum oxide.

The resin composition of the present invention is mainly used as a delayed tack type adhesive, but is also useful as a hot melt adhesive or the like.

The substrate of the present invention preferably has a film, sheet or tape shape, and examples of the material include paper, plastic, wood, cloth, non-woven fabric and metal.

As a means for applying the thermoplastic resin composition of the present invention as an adhesive to a substrate such as paper, it is desirable to apply the resin composition of the present invention as an aqueous dispersion (emulsion). Alternatively, the resin composition may be dissolved in an organic solvent and applied, or the resin composition of the present invention may be directly heated and melted and applied. When preparing an aqueous dispersion, there are a method of premixing the composition to disperse it in water, a method of dispersing a solid plasticizer and a crystallization retarder in a thermoplastic resin emulsion and a tackifier emulsion, and a solid plasticizer in the emulsion. As a method of dispersing the agent, the crystallization retarder, a molten (c) solid plasticizer, (d) a method of dispersing the crystallization retarder, (c) solid plasticizer, (d) crystallization retarder Method of dispersing while making fine powder, (c) solid plasticizer made into fine powder, (d) method of dispersing crystallization retarder, solid plasticizer (c) aqueous dispersion, crystallization retarder (d) water dispersion There is a method of mixing liquids. Among them, the fine powder of the solid plasticizer (c) and the fine powder of the crystallization retarder (d) are methods by which the state of the mixture can be taken, that is, the solid plasticizer (c) and the crystallization retarder (d) are finely divided. A method of dispersing while forming a powder, a fine powdered solid plasticizer (c), a method of dispersing a crystallization retarder (d), a solid plasticizer (c) aqueous dispersion, a crystallization retarder (d) water dispersion Is preferred.

For coating, a gravure coater, a call coater, a bar coater or the like can be used.

The adhesive base material of the present invention is preferably a thin piece member such as paper, plastic, metal or non-woven fabric coated with an adhesive agent. Specifically, it is a liquor bottle, a soft drink bottle / can, Labels for shampoo bottles, pharmaceutical bottles, motor oil cans, stationery boxes, and other glass, plastic, metal, and wood, but also adhesive tape, patch, iron print, etc.

Next, in order to further clarify the characteristics of the present invention, a specific description will be given with reference to examples. In addition, "part" in the sentence
All "%" indicate weight basis.

[0028]

【Example】

Example 1 200 parts of styrene / acrylic emulsion (solid content 50%) as a thermoplastic resin, 40 parts of rosin ester emulsion (solid content 50%) as a tackifier, and di2-phenylethyl terephthalate (TP) as a solid plasticizer.
A / PhEt: melting point 108 ° C.) 80 parts, tribenzyl trimellitate (TMA / Bz: melting point 89 ° C.) 40 parts as a crystallization retarder, and water 120 parts were mixed to prepare a heat-sensitive delayed tack adhesive. . This adhesive was coated on a high-quality paper so as to have a solid content of 15 g / m ² and then dried at 40 ° C. for 2 minutes to obtain a heat-sensitive delayed tack type adhesive sheet. This sheet was evaluated for blocking resistance and adhesiveness. This is shown in Table 1.

Example 2 As a thermoplastic resin, an acrylic emulsion (solid content 5
0%) 200 parts, di2-phenylethyl terephthalate (TPA / PhEt: melting point 108 ° C.) as a solid plasticizer
Example 1 was repeated except that 90 parts, 30 parts of pentaerythritol tetrabenzoate (Pent / Bz: melting point 96 ° C.) as a crystallization retarder and 120 parts of water were used.

Example 3 70 parts of di2-phenoxyethyl isophthalate (IPA / PhOEt: melting point 77 ° C.) as a solid plasticizer, 30 parts of pentaerythritol tetrabenzoate (Pent / Bz: melting point 96 ° C.) as a crystallization retarder, and Water 100
The same procedure was performed as in Example 2 except that parts were used.

Example 4 Tribenzyl trimellitate (TMA) as a solid plasticizer
/ Bz: melting point 89 ° C.) 100 parts, pentaerythritol tetrabenzoate (Pent / B as a crystallization retarder)
(z: melting point 96 ° C.) 50 parts and water were used in the same manner as in Example 2 except that 150 parts were used.

Example 5 As a crystallization retarder, a bisphenol A ethylene oxide (2 mol) adduct dibenzoate (BPE / Bz:
Example 4 was repeated except that 30 parts of a melting point of 92 ° C.) and 130 parts of water were used.

Example 6 The procedure of Example 3 was repeated, except that 30 parts of ditrimethylolpropane tetrabenzoate (DTMP / Bz: melting point 77 ° C.) was used as a crystallization retarder.

Example 7 Example 4 was repeated except that 200 parts of styrene / acrylic emulsion (solid content 50%) was used as the thermoplastic resin.

Example 8 Styrene-butadiene copolymer (SBR) emulsion (styrene / butadiene = 70) as a thermoplastic resin
/ 30%, solid content 50%) 200 parts, rosin ester emulsion as tackifier (solid content 50%) 60
Part, tribenzyl trimellitate (T
MA / Bz: melting point 89 ° C.) 120 parts, pentaerythritol tetrabenzoate (Pent as a crystallization retarder)
/ Bz: melting point 96 ° C.) 40 parts and water 160 parts were mixed to prepare a heat-sensitive delayed tack adhesive. This pressure sensitive adhesive was coated on a high-quality paper so that the solid content was 15 g / m ^2, and then dried at 40 ° C. for 2 minutes to obtain a heat-sensitive delayed tack type pressure-sensitive adhesive sheet. This sheet was evaluated for blocking resistance and adhesiveness.

Comparative Example 1 Dicyclohexyl phthalate (DCH as a solid plasticizer
(P: melting point 63 ° C.) 120 parts and no crystallization retarder was used, and the same procedure as in Example 1 was carried out. This is shown in Table 2.

Comparative Example 2 Comparative Example 1 was repeated except that 120 parts of di2-phenylethyl terephthalate (TPA / PhEt: melting point 108 ° C.) was used as a solid plasticizer. This is shown in Table 2.

Comparative Example 3 The same procedure as in Example 3 was carried out except that 100 parts of di2-phenoxyethyl isophthalate (IPA / PhOEt: melting point 77 ° C.) was used as a solid plasticizer and no crystallization retarder was used. This is shown in Table 2.

Comparative Example 4 Tribenzyl trimellitate (TMA) was used as a solid plasticizer.
/ Bz: melting point 89 ° C.) (150 parts) and no crystallization retarder was used, and the same procedure as in Example 4 was performed. Table 2
It was shown to.

[Evaluation Method] Blocking resistance: The pressure-sensitive adhesive sheet was heated at 60 ° C. or 65 ° C. for 1 hour, and the surface tackiness immediately after it was evaluated by touch with a finger. (○
If so, it was passed) ○: No tackiness △: Some tackiness ×: There is tackiness

Adhesiveness: The pressure-sensitive adhesive sheet was ironed on the surface at 130 ° C.
Heat for 10 seconds, and after 30 seconds, stick it on the cardboard 1
The adhesiveness after one day and after one month was evaluated by touching with fingers. (Passed if ◯) ○: Adhesive strength is sufficient Δ: Adhesive strength is low ×: Adhesive strength is poor [Crystallization time of mixture of solid plasticizer and crystallization retarder] Sample 2 g After heating and melting Cooling at room temperature <Crystallization time of solid plasticizer> -TPA / PhEt 6 minutes-IPA / PhOEt 7 hours-TMA / Bz 10 days-DCHP 25 days

<Crystallization Time of Solid Plasticizer / Crystal Delaying Agent Mixture> ・ (IPA / PhOEt) / (TMA / Bz) = 7/3 2 days ・ (IPA / PhOEt) / (DTMP / Bz) = 7 / 3 3 days ・ (IPA / PhOEt) / (Pent / Bz) = 7/3 2 days ・ (IPA / PhOEt) / (BPE / Bz) = 7/3 4 days In the table, solid plasticizer / crystallization The crystallization delay ratio when the retarder = 7/3 is shown.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

The specific crystallization retarder of the present invention is added to a heat-sensitive delayed-tack type thermoplastic resin composition to give the thermoplastic resin composition an adhesive property as a pressure-sensitive adhesive,
Both of them have excellent blocking resistance. When this is used as a pressure-sensitive adhesive, a good thermosensitive delayed tack type pressure-sensitive adhesive base material can be obtained. Its adhesive substrates, such as liquor bottles, soft drink bottles, shampoo bottles, pharmaceutical bottles,
It has an extremely high industrial utility value as an adhesive for labels such as motor oil cans and stationery boxes.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C09J 7/02 JJC C09J 7/02 JJT JKK JKK 201/00 JAW 201/00 JAW

Claims (14)

[Claims] 1. A crystallization retarder for a solid plasticizer, which has a property of doubling the crystallization time until recrystallization when mixed with 30% by weight of the solid plasticizer and melted. . 2. A polyester compound comprising a polyhydric alcohol and an aromatic monobasic acid and / or a polyester compound comprising an aromatic group-substituted alkyl alcohol and a polybasic acid. Crystallization retarder 3. The crystallization retarder according to claim 1, wherein the multiester compound is solid. 4. The crystallization retarder according to claim 2, wherein the polyhydric alcohol is an aliphatic polyhydric alcohol. 5. The crystallization retarder according to claim 2, wherein the polyhydric alcohol is a compound having a bisphenol skeleton. 6. The crystallization retarder according to claim 2, wherein the aromatic group-substituted alkyl alcohol is benzyl alcohol. 7. (a) thermoplastic resin, (b) tackifier, (c)
A thermoplastic resin composition comprising a solid plasticizer and (d) a crystallization retarder according to claim 1. 8. The solid plasticizer (c) is a polyester compound comprising an aromatic group-substituted alkyl alcohol and a polybasic acid, and the crystallization retarder (d) is a polyhydric alcohol and an aromatic monobase. The thermoplastic resin composition according to claim 7, which is a polyester compound comprising an acid. 9. The thermoplastic resin composition according to claim 7, wherein the thermoplastic resin (a) is an emulsion type thermoplastic resin. 10. A mixture of a fine powder of the solid plasticizer (c) and a fine powder of the crystallization retarder (d) according to claim 1, which is a compound different from the solid plasticizer (c). And a solid plasticizer composition. 11. A thermoplastic resin composition comprising the solid plasticizer composition according to claim 10. 12. A pressure-sensitive adhesive comprising the thermoplastic resin composition according to claim 7. 13. A heat-sensitive delayed tack type pressure-sensitive adhesive base material, which is obtained by applying the pressure-sensitive adhesive according to claim 12 to a base material. 14. The pressure-sensitive adhesive substrate according to claim 13, which is a label.