WO2019044637A1 - Composition de résine adhésive, et film protecteur mettant en œuvre celle-ci - Google Patents

Composition de résine adhésive, et film protecteur mettant en œuvre celle-ci Download PDF

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Publication number
WO2019044637A1
WO2019044637A1 PCT/JP2018/031074 JP2018031074W WO2019044637A1 WO 2019044637 A1 WO2019044637 A1 WO 2019044637A1 JP 2018031074 W JP2018031074 W JP 2018031074W WO 2019044637 A1 WO2019044637 A1 WO 2019044637A1
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Prior art keywords
weight
resin composition
resin
polymer block
aromatic alkenyl
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PCT/JP2018/031074
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English (en)
Japanese (ja)
Inventor
藤野　英俊
大木　祐和
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東洋紡株式会社
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Application filed by 東洋紡株式会社 filed Critical 東洋紡株式会社
Priority to JP2019539420A priority Critical patent/JP7264053B2/ja
Priority to KR1020207008737A priority patent/KR102590488B1/ko
Priority to CN201880057145.1A priority patent/CN111051460B/zh
Publication of WO2019044637A1 publication Critical patent/WO2019044637A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/06—Butadiene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
    • C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C08F297/04—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type polymerising vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/098—Metal salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/20—Carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/04—Condensation polymers of aldehydes or ketones with phenols only
    • C08L61/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • C08L61/14—Modified phenol-aldehyde condensates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/40—Adhesives in the form of films or foils characterised by release liners

Definitions

  • the present invention relates to a pressure-sensitive adhesive composition and a protective film having a pressure-sensitive adhesive layer formed therefrom. Specifically, when the protective film is stored in a roll state and then the film is fed out, the film does not partially stretch or deform, and the processability is excellent, and further, the adhesion to the adherend and the releasability
  • the present invention relates to a tacky resin composition excellent in the above and a protective film having a pressure sensitive adhesive layer.
  • the protective film is formed by stacking and storing members such as prism sheets used for optical applications, synthetic resin plates used for building material applications, stainless steel plates, aluminum plates, decorative plywood, steel plates, and glass plates, It has been used to protect against damage during transport or secondary processing such as bending or pressing. It has also been used to protect household appliances, precision machines, and scratches during transport in the manufacturing process.
  • Such a protective film should have good adhesiveness and be able to be easily peeled off after use without contaminating the surface of the adherend with an adhesive.
  • the number of adherends has been diversified, and there are many cases where the coated surface is smooth and the surface has irregularities.
  • the back surface of the prism sheet is smooth as compared to the prism surface having large surface irregularities, but a back surface having fine surface irregularities is formed, and the light of the backlight is diffused uniformly, and with other members.
  • the function of preventing interference due to close contact and making appearance defects such as flaws inconspicuous are added.
  • the back surface of the prism sheet needs to have a good adhesion to the back surface in order to be protected by the protective film when stacked, stored or transported.
  • the problem of a raise of adhesive force (what is called adhesive sticking) arose, and there existed a problem of becoming difficult to peel off. It is known that this is due to the product to which the protective film is attached is made more prominent by being exposed to high temperatures during transport and storage.
  • a polymer block consisting of a continuous series of aromatic alkenyl compound units, which are considered to be relatively resistant to adhesion growth, and mainly composed of aromatic alkenyl compound units
  • a copolymer comprising an aromatic alkenyl-conjugated diene monomer copolymer block randomly containing a diene monomer unit and an aromatic alkenyl compound unit is used for the adhesive layer (for example, a patent)
  • the literature 1 etc. is sufficient, the protective performance with respect to a to-be-adhered body is sufficient, but the ease of peeling from a to-be-adhered body and the ease of delivery of the protective film from a roll state were not compatible.
  • the object of the present invention is to store the protective film in a roll state and then to unroll the film partially without stretching or deforming the film, so that the processability is excellent, and the back surface of the prism sheet When attached to an adherend with fine surface irregularities, it has sufficient adhesion, and adhesion is difficult to develop even when exposed to high temperatures during transport and storage, etc., and the protective film is peeled off. No adhesive residue occurs on the adherend later, and the function is to be maintained.
  • the present invention is a tacky resin composition containing a block copolymer satisfying the following 1) and 2) as a main component and containing an ⁇ -methylstyrene resin and a terpene resin.
  • a block copolymer comprising the following polymer block A and the following polymer block B and having a structural formula ABA and / or a structural formula AB.
  • Polymer block A A polymer block composed mainly of units derived from aromatic alkenyl compound units and composed mainly of units derived from aromatic alkenyl compound monomer units
  • Polymer block B Conjugated diene Aromatic alkenyl monomer-conjugated diene monomer copolymer block randomly containing units derived from monomeric units and aromatic alkenyl compound monomeric units 2)
  • the conjugated diene in the polymer block B The hydrogenation rate of the double bond derived from the monomer unit is 90 mol% or more.
  • the conjugated diene monomer unit is preferably a butadiene monomer unit.
  • the terpene resin contains a terpene phenol resin.
  • 0.1 to 30 parts by weight of the terpene phenol resin is contained with respect to 100 parts by weight of the block copolymer.
  • the organic lubricant is ethylenebisstearic acid amide and / or calcium stearate.
  • the protective film which has a base material layer which consists of an adhesive layer which consists of the said adhesive resin composition, and a polypropylene resin composition is suitable.
  • a protective film having a release layer on the side opposite to the adhesive layer is preferred.
  • the protective film is suitably used to protect the back surface of the prism sheet.
  • the film when the protective film is stored in a roll state and then the film is fed out, the film does not partially elongate or deform, and the processability is excellent, and further the prismatic sheet
  • the film When pasted to an adherend with fine surface irregularities as in the back surface, it has sufficient adhesion, and adhesion is unlikely to develop even if exposed to high temperatures during transport and storage, etc. Even after peeling the film, no adhesive residue occurs on the adherend, and the function can be maintained.
  • the block copolymer in the present invention is a block copolymer containing the following polymer block A and the following polymer block B.
  • Polymer block A A polymer block comprising a unit derived from an aromatic alkenyl compound monomer unit as a main repeating unit and mainly comprising a unit derived from an aromatic alkenyl compound monomer unit :
  • An aromatic alkenyl compound monomer-conjugated diene monomer copolymer block which randomly contains a unit derived from a conjugated diene monomer unit and an aromatic alkenyl compound monomer unit
  • the block copolymer of the present invention is a block copolymer containing the above-described polymer block A and polymer block B and having the structural formula ABA and / or AB.
  • the block copolymer of the present invention is an aromatic alkenyl compound monomer-conjugated diene monomer copolymer block which randomly contains units derived from conjugated diene monomer units and aromatic alkenyl compound monomer units.
  • the protective film is attached to an adherend having finer surface irregularities than that of the other block copolymers by having a certain polymer block B, and then it is exposed at high temperature during its transportation and storage But it's hard to happen.
  • the content rate of the unit derived from the aromatic alkenyl compound monomeric unit in a block copolymer is 30 weight% or more. If the content of the unit derived from the aromatic alkenyl compound monomer unit is 30% by weight or more, the initial tackiness is too strong, adhesive residue is generated, or the tackiness is hardly promoted, and 40% by weight or more Is more preferable, and 45% by weight or more is more preferable. When the content of the unit derived from the aromatic alkenyl compound monomer unit is 60% by weight or less, initial tack can be easily obtained, and 55% by weight or less is more preferable.
  • the content (St (A + B)) of the unit derived from the aromatic alkenyl compound monomer in the block copolymer represents a numerical value defined by the following formula.
  • the content of units derived from such aromatic alkenyl compound monomer units is determined by 1 H-NMR. Further, the content ratio of units derived from such aromatic alkenyl compound monomer units can also be determined by infrared spectroscopy, and values approximately equivalent to 1 H-NMR can be obtained.
  • St (A + B) (mass of unit derived from aromatic alkenyl compound monomer unit in block copolymer) / (mass of total unit derived from monomer in block copolymer) ⁇ 100 (% by weight )
  • the weight average molecular weight of the block copolymer is preferably 30,000 to 200,000. When the weight average molecular weight is 200,000 or less, adhesion to adherends having fine surface irregularities can be easily obtained, solubility in solvents and heat melting properties are improved, and industrial processing into pellets or Film production by melt coextrusion may also be facilitated.
  • the weight average molecular weight of the block copolymer is more preferably 180,000 or less. When the weight average molecular weight is 30,000 or more, the polymer may not easily adhere to the production equipment or the like in the step of removing the solvent and drying the polymer, and industrial production may be facilitated.
  • the weight average molecular weight of the block copolymer is more preferably 100,000 or more, and still more preferably 130,000 or more.
  • the melt flow rate (MFR) value of the block copolymer is preferably in the range of 0.1 to 20 g / min, and more preferably 1 to 15 g / min.
  • MFR melt flow rate
  • the melt flow rate value is less than 0.1 g / min, the solubility in a solvent during polymerization may be deteriorated, the heat melting property may be lowered, and it may be difficult to take out the polymer from the production equipment. This difficulty is a problem that may recur even during film deposition.
  • the melt flow rate value is more preferably 2 g / min or more, further preferably 3 g / min or more.
  • the melt flow rate value is more than 20 g / min, the polymer adheres and remains inside the production equipment and the like in the step of removing the solvent and drying, and it becomes difficult to take out the polymer. This difficulty is a problem that may recur even during film deposition.
  • the melt flow rate value is more preferably 10 g / min or less, still more preferably 6 g / min or less.
  • the polymer block A in the present invention comprises a unit derived from an aromatic alkenyl compound monomer unit as a main repeating unit, and is a polymer block mainly composed of a unit derived from an aromatic alkenyl compound monomer unit
  • the content of the unit derived from the aromatic alkenyl compound monomer unit in the polymer block A is preferably 80% by weight or more.
  • the thermoplasticity of the adhesive resin composition can be suppressed, and the adhesive force of the adhesive resin composition
  • the unit derived from the aromatic alkenyl compound monomer unit in the polymer block A is more preferably 90% by weight or more.
  • repeating units other than units derived from aromatic alkenyl compound monomer units may be contained in a range of less than 20% by weight.
  • the aromatic alkenyl compound monomer unit is not particularly limited, and examples thereof include styrene, tert-butylstyrene, ⁇ -methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylethylene, Mention may be made of aromatic alkenyl monomer units such as vinyl naphthalene, vinyl anthracene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and vinylpyridine.
  • the repeating unit other than the unit derived from the aromatic alkenyl compound monomer unit is a repeating unit derived from the compound copolymerizable with the unit derived from the aromatic alkenyl compound monomer unit, for example, a conjugated diene compound or Mention may be made of repeating units derived from (meth) acrylic acid ester compounds. Among them, 1,3-butadiene and isoprene are preferable because they have high copolymerizability with the unit derived from the aromatic alkenyl compound unit.
  • the content of the polymer block A in the block copolymer is required to be 10% by weight or more. If the content of the polymer block A is less than 10% by weight, the initial tackiness may be too strong, and adhesive residue may occur, or the tackiness may be easily promoted. On the other hand, the content of the polymer block A in the block copolymer is preferably 50% by weight or less. If it exceeds 50% by weight, initial tack may not be observed. More preferably, it is 45% by weight or less, still more preferably 40% by weight or less.
  • the polymer block B in the present invention is an aromatic alkenyl monomer-conjugated diene monomer copolymer which randomly contains a unit derived from a conjugated diene monomer unit and a unit derived from an aromatic alkenyl compound monomer unit. It is a polymer block.
  • a protective film using the adhesive resin composition of the present invention is attached to an adherend having fine surface irregularities. After application, even when exposed to high temperatures during transport and storage, adhesion growth is less likely to occur.
  • the aromatic alkenyl compound monomer unit is not particularly limited, and examples thereof include styrene, tert-butylstyrene, ⁇ -methylstyrene, p-methylstyrene, p-ethylstyrene, divinylbenzene, 1,1-diphenylethylene, Mention may be made of aromatic vinyl monomer units such as vinyl naphthalene, vinyl anthracene, N, N-dimethyl-p-aminoethylstyrene, N, N-diethyl-p-aminoethylstyrene and vinylpyridine.
  • the conjugated diene monomer unit in the polymer block B in the present invention is not particularly limited, and examples thereof include 1,3-butadiene, 1,2-butadiene, isoprene, 2,3-dimethyl-butadiene, and 1,3-butadiene.
  • diolefins preferred is at least one unit selected from 1,3-butadiene units or isoprene units, which have high polymerization reactivity and easy availability of raw materials. Furthermore, to obtain high mechanical strength, it is more preferable to select 1,3-butadiene units.
  • the hydrogenation rate of the double bond derived from the conjugated diene monomer unit in the block copolymer B in the present invention is 90 mol% or more. Preferably it is 95 mol% or more, more preferably 98 mol% or more. If the amount is less than 90 mol%, not only adhesion to an adherend having fine asperities can not be obtained, but also heat resistance and weatherability are concerned.
  • the content of the unit derived from the aromatic alkenyl compound monomer unit in the block copolymer B is preferably 10% by weight or more. If the content of the unit derived from the aromatic alkenyl compound monomer unit is less than 10% by weight, the initial tack may be too strong, adhesive residue may occur, or the tack may be easily promoted. 20 weight% or more is more preferable, and, as for the content rate of the unit derived from an aromatic alkenyl compound monomer unit, 30 weight% or more is especially preferable. On the other hand, the content of the unit derived from the aromatic alkenyl compound monomer unit is preferably 80% by weight or less. If it exceeds 80% by weight, initial tack may not be observed. As for the content rate of the unit derived from an aromatic alkenyl compound monomer unit, 50 weight% or less is more preferable, and 40 weight% or more is especially preferable.
  • the ⁇ -methylstyrene resin As a result of intensive investigations, the ⁇ -methylstyrene resin, combined with the terpene resin, suppresses the adhesion development of the pressure-sensitive adhesive layer, and the surface of the substrate layer opposite to the surface of the pressure-sensitive adhesive layer or the surface of the release layer and the surface of the pressure-sensitive adhesive layer It has been found that it has the effect of improving the releasability of the film and that the initial tack can be sufficiently obtained. This is presumed to be due to the diffusion of the ⁇ -methylstyrene resin into the polymer block B of the block copolymer.
  • the ⁇ -methylstyrene resin used in the present invention is mainly composed of ⁇ -methylstyrene homopolymer and / or ⁇ -methylstyrene, styrene and p-methylstyrene, p-chlorostyrene, chloromethylstyrene, Copolymers comprising two or more styrenic compounds such as tert-butylstyrene, p-ethylstyrene, divinylbenzene and the like can be mentioned.
  • the ⁇ -methylstyrene resin may be a copolymer with an aliphatic monomer.
  • the molecular weight Mw is preferably 4,000 or more from the viewpoint of resin strength and bleed out.
  • a copolymer comprising two or more monomers it may be a block copolymer or a random copolymer. Among them, those having a softening point of 100 ° C. or more are preferable, and those of 150 ° C. or more are more preferable.
  • Terpene resin In the present invention, terpene resin or its hydrogenated substance is mentioned.
  • Terpene-based resins are obtained by cationic polymerization using terpene-based compounds (eg, ⁇ -pinene, ⁇ -pinene, limonene, etc.) collected from the epidermis of pine trees and oranges as a raw material.
  • the terpene resin is roughly classified into a polyterpene resin which is a polymer of terpene monomer, an aromatic modified terpene resin obtained by copolymerizing a terpene monomer and an aromatic monomer, a terpene phenol resin which is obtained by reacting a terpene monomer and phenols, Are classified as hydrogenated terpene resins obtained by hydrogenating these.
  • the terpene resin is a hydrogenated resin, the concern of discoloration at high temperatures or with time can be reduced.
  • the terpene resins may be used alone or in combination of two or more.
  • the glass transition temperature or softening point of the terpene resin is preferably 30 ° C. or more. If the temperature is 30 ° C.
  • the glass transition temperature or softening point of the terpene resin is preferably 50 ° C. or higher, more preferably 65 ° C. or higher, and particularly preferably 90 ° C. or higher, in consideration of high temperature retardancy.
  • the terpene resin can be expected to be improved in adhesion strength and suppression of growth by the combination of ⁇ -methylstyrene with the effect of plasticizing the adhesive resin composition and the effect of inhibiting the molecular motion of the adhesive resin.
  • terpene resins terpene phenol resins are preferable, and hydrogenated terpene phenol resins are particularly preferable. Since the phenol group of the terpene phenol resin has an electrical affinity to the adherend, the product to which the protective film is attached is unlikely to increase its adhesion even when exposed to high temperatures during transport and storage etc., and is stable High adhesion is expected.
  • the combination with an ⁇ -methylstyrene-based resin can sufficiently exhibit the effect of suppressing adhesion growth and initial adhesion. Also in the case of terpene phenol resin, the hydrogenation can reduce the concern of discoloration due to high temperature and aging.
  • the adhesive resin composition of the present invention is mainly composed of the block copolymer described in paragraph 0020, and contains an ⁇ -methylstyrene resin and a terpene resin.
  • the main component means that 50% by weight or more is contained in the adhesive resin composition.
  • the amount of the ⁇ -methylstyrene resin is 1 part by weight or more with respect to 100 parts by weight of the block copolymer, adhesion growth of the block copolymer is easily suppressed, and when it is 50 parts by weight or less, the adhesion to the adherend Is hard to lower.
  • the amount of the ⁇ -methylstyrene resin is 10 parts by weight or more based on 100 parts by weight of the block copolymer, adhesion promotion of the block copolymer is more easily suppressed, and when it is 40 parts by weight or less, adhesion with the adherend Power is less likely to decline.
  • the terpene resin it is preferable to contain 1 to 50 parts by weight of the terpene resin with respect to 100 parts by weight of the block copolymer.
  • the content of the terpene resin is 1 part by weight or more, an improvement in initial tack is observed. More preferably, it is 3 parts by weight or more, still more preferably 5 parts by weight, and particularly preferably 15 parts by weight or less. If the content of the terpene resin is 50 parts by weight or less, the compatibility with the adhesive resin composition does not decrease, and a decrease in initial adhesive strength is hardly observed. More preferably, it is 40 parts by weight or less, still more preferably 30 parts by weight or less, and particularly preferably 25 parts by weight or less.
  • the adhesive resin composition of the present invention may, if necessary, be an organic lubricant, an antioxidant, a light stabilizer, or an ultraviolet light absorber.
  • Organic lubricant used in the present invention is preferably a saturated fatty acid bisamide or a fatty acid metal salt in consideration of excessive exudation at room temperature or high temperature.
  • Specific examples thereof include ethylenebisstearic acid bisamide and metal stearates. These may be used alone or in combination of two or more.
  • the organic lubricant is preferably contained in an amount of 0.1 to 2 parts by weight with respect to 100 parts by weight of the block copolymer.
  • the organic lubricant can be expected to have the effect of suppressing the progress of adhesion.
  • the content of the organic lubricant is 0.1 parts by weight or more, it is easy to suppress the progress of adhesion at high temperature or with time, and it is more preferable that the content is 0.2 parts by weight or more.
  • the content of the organic lubricant is 2 parts by weight or less, bleed out at high temperature or with time is difficult to occur, and there is no concern of contaminating the adherend, but it is more preferably 1 part by weight or less It is particularly preferred that it is not more than part by weight.
  • the organic lubricant used in the present invention preferably has a high melting point in view of bleed out at high temperature or with time, and specific examples thereof include ethylenebisstearic acid amide and calcium stearate.
  • the antioxidant used in the present invention is not particularly limited, and examples thereof include commonly used ones such as phenol type (monophenol type, bisphenol type, polymer type phenol type), sulfur type, and phosphorus type.
  • Light stabilizer examples of the light stabilizer used in the present invention include hindered amine compounds.
  • UV absorber The ultraviolet absorber used in the present invention is not particularly limited, and examples thereof include salicylic acid type, benzophenone type, benzotriazole type, cyanoacrylate type and the like.
  • Softening agents are low melting point conjugated polymers having a melting point of 50 ° C. or lower, petroleum oils or fats having a low melting point, or natural oils and fats, and examples thereof include low molecular weight diene polymers, polyisobutylene, hydrogenated polyisobutylene, hydrogenated Polybutadiene, paraffinic process oil, naphthenic process oil, aromatic process oil, castor oil, tall oil, natural oil, liquid polyisobutylene resin, polybutene, or hydrogenated products of these or the like can be used. These softeners may be used alone or in combination of two or more.
  • filler examples include calcium carbonate, magnesium carbonate, silica, zinc oxide, titanium oxide and the like.
  • the protective film which concerns on this invention is obtained by laminating
  • the pressure-sensitive adhesive layer in the present invention is composed of the above-mentioned pressure-sensitive adhesive composition, and the thickness is usually about 1 to 30 ⁇ m, preferably 2 to 10 ⁇ m.
  • the base material layer in the present invention can be formed of a polyolefin resin.
  • the polyolefin resin contained in the substrate is not particularly limited, and ethylene homopolymers, ethylene- ⁇ -olefin copolymers, ethylene- (meth) acrylic acid copolymers, ethylene- (meth) acrylic acid ester co-polymers Polymer and polyethylene-based resin such as ethylene-vinyl acetate copolymer; Propylene homopolymer, polypropylene- ⁇ -olefin copolymer, and polypropylene-based resin such as propylene-ethylene copolymer; butene homopolymer; butadiene And homopolymers or copolymers of conjugated dienes such as isoprene.
  • polyethylene-type resin high density polyethylene, medium density polyethylene, low density polyethylene etc. are mentioned as said polyethylene-type resin.
  • the form of the copolymerization may be random, may be a block, or may be in the form of a terpolymer.
  • the polyolefin resins may be used alone or in combination of two or more.
  • the said polyethylene-type resin is obtained using ethylene as a main component.
  • the proportion of structural units derived from ethylene is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably 90% by weight or more in 100% by weight of the total structural units of the polyethylene resin.
  • the said polypropylene resin is obtained using propylene as a main component.
  • the proportion of structural units derived from propylene is preferably 50% by weight or more, more preferably 70% by weight or more, and still more preferably 90% by weight or more in 100% by weight of the total structural units of the polypropylene resin.
  • the base material layer of the present invention is mainly made of a polypropylene-based resin in terms of heat resistance, weather resistance, or adhesion with an adhesive layer.
  • the thickness of the base material layer in the present invention is preferably 10 ⁇ m or more, more preferably 100 ⁇ m or less.
  • the handleability of a protective film becomes it still higher that the thickness of the above-mentioned substrate is 10 micrometers or more and 100 micrometers or less.
  • the surface asperity is imparted to suppress the peeling force between the surface of the base material layer and the surface of the pressure-sensitive adhesive layer. It is preferable to reduce the contact area with the adhesive layer.
  • the average surface roughness SRa of the surface of the release layer is preferably 0.40 ⁇ m or more.
  • the average surface roughness of the surface is more preferably 0.85 ⁇ m or less in SRa, and more preferably 0.50 ⁇ m or more and 0.70 ⁇ m or less.
  • the protective performance and the peeling force of the adherend can be improved.
  • the surface roughness of the release layer is lower than 0.40 ⁇ m, the delivery property of the film when the film is in roll form is deteriorated.
  • the surface roughness of the base material layer is higher than 0.85 ⁇ m, the surface irregularities of the base material layer may be transferred to the surface of the adhesive layer, and the adhesion may be significantly reduced.
  • the average surface roughness SRa In order to set the average surface roughness SRa to 0.40 ⁇ m or more, it is preferable to add a resin incompatible with homopolypropylene or random polypropylene as a resin used for the base material layer, or a propylene-ethylene block copolymer. It can be used for When a propylene-ethylene block copolymer is used, the asperity state hardly changes due to the change of the production machine base or the melt-kneading conditions at the time of film formation, and stable production is possible.
  • the average surface roughness SRa can be increased by increasing the molecular weight of ethylene-propylene rubber or increasing the amount of ethylene in the propylene-ethylene block copolymer.
  • the average surface roughness SRa can be further increased by mixing an incompatible resin with the propylene-ethylene block copolymer.
  • the average surface roughness SRa can also be increased by lowering the shear rate applied to the resin or increasing the residence time in the extrusion step described later.
  • it is effective to mix a homo-polypropylene resin with a propylene-ethylene block copolymer.
  • an ⁇ -olefin (co) polymer having 4 or more carbon atoms such as 4-methylpentene-1 (co) polymer can be suitably used.
  • low density polyethylene, high density polyethylene, copolymer of ethylene and a small amount of ⁇ -olefin, copolymer of ethylene and vinyl acetate, polystyrene, alicyclic olefin resin, polyester resin, polyamide resin, etc. can be mentioned.
  • 4-methylpentene-1 (co) polymers are preferable because they not only roughen the surface in a matte state, but also can reduce the peeling force by lowering the surface free energy of the film surface.
  • the compounding amount of the ⁇ -olefin (co) polymer having 4 or more carbon atoms in the base material layer (resin component constituting the base material layer) is in the range of 0% by weight or more and 35% by weight or less.
  • the content of the ⁇ -olefin (co) polymer having 4 or more carbon atoms exceeds 35% by weight, the raw materials of the base material layer and the adhesive layer are laminated by coextrusion using a T die or the like. The film forming property of the layer is deteriorated.
  • the release layer in the present invention can be provided on the base material layer opposite to the adhesive layer. As a result, by dispersing the functions in each of the base material layer and the release layer, it is possible to cope with a wider range of uses.
  • the average surface roughness SRa of the surface of the release layer is preferably 0.40 ⁇ m or more.
  • the average surface roughness of the surface is more preferably 0.850 ⁇ m or less in SRa, and more preferably 0.500 ⁇ m or more and 0.700 ⁇ m or less.
  • the protection performance and the peeling force of the adherend can be improved.
  • the surface roughness of the release layer is lower than 0.40 ⁇ m, the delivery property of the film when the film is in roll form is deteriorated.
  • the surface roughness of the release layer is higher than 0.850 ⁇ m, the surface irregularities of the release layer may be transferred to the surface of the adhesive layer, and the adhesion may be significantly reduced.
  • the average surface roughness SRa 0.40 ⁇ m or more, it is preferable to add a resin incompatible with homopropylene or random polypropylene as a resin used for the releasing layer, or a propylene-ethylene block copolymer. It can be used for When a propylene-ethylene block copolymer is used, the asperity state hardly changes due to the change of the production machine base or the melt-kneading conditions at the time of film formation, and stable production is possible.
  • the average surface roughness SRa can be increased by increasing the molecular weight of ethylene-propylene rubber or increasing the amount of ethylene in the propylene-ethylene block copolymer.
  • the average surface roughness SRa can be further increased by mixing an incompatible resin with the propylene-ethylene block copolymer.
  • the average surface roughness SRa can also be increased by lowering the shear rate applied to the resin or increasing the residence time in the extrusion step described later.
  • it is effective to mix a homo-polypropylene resin with a propylene-ethylene block copolymer.
  • an ⁇ -olefin (co) polymer having 4 or more carbon atoms such as 4-methylpentene-1 (co) polymer can be suitably used.
  • Other examples include low density polyethylene, high density polyethylene, copolymer of ethylene and a small amount of ⁇ -olefin, copolymer of ethylene and vinyl acetate, polystyrene, polyester resin, polyamide resin and the like.
  • 4-methylpentene-1 (co) polymers are preferable because they not only roughen the surface in a matte state, but also can reduce the peeling force by lowering the surface free energy of the film surface.
  • the compounding amount of the ⁇ -olefin (co) polymer having 4 or more carbon atoms in the release layer is in the range of 0% by weight to 35% by weight. If the content of the ⁇ -olefin (co) polymer having 4 or more carbon atoms exceeds 35% by weight, the base layer and the pressure-sensitive adhesive layer are coextruded to form a laminate, thereby deteriorating the film forming property of the base layer.
  • the thickness of the release layer is not particularly limited.
  • the thickness of the release layer is preferably 2 ⁇ m or more, preferably 10 ⁇ m or less.
  • the handleability of a protective film becomes it still higher that the thickness of the said release layer is 2 micrometers or more and 10 micrometers or less.
  • the initial adhesive strength of the protective film of the present invention is preferably 3 cN / 25 mm or more and 20 cN / 25 mm or less. When it is 3 cN / 25 mm or more, it does not separate or float during handling or transportation, and when it is less than 20 cN / 25 mm, no excessive force is required when it is peeled off. More preferably, they are 4 cN / 25 mm or more and 15 cN / 25 mm or less. More preferably, they are 5 cN / 25 mm or more and 10 cN / 25 mm or less.
  • the initial tack was measured as follows.
  • the adhesion progression rate of the protective film of the present invention is preferably 400% or less.
  • the peeling operation can be performed under more constant conditions, so that the working efficiency is improved. More preferably, it is 300% or less, more preferably 200% or less.
  • the adhesion with time of the protective film of the present invention is preferably 3 cN / 25 mm or more and 40 cN / 25 mm or less.
  • it is 3 cN / 25 mm or more, it does not separate or float during handling or transportation, and when it is 40 cN / 25 mm or less, no excessive force is required when it is peeled off.
  • they are 4 cN / 25 mm or more and 40 cN / 25 mm or less. More preferably, it is 5 cN / 25 mm or more and 30 cN / 25 mm or less, and particularly preferably 5 cN / 25 mm or more and 20 cN / 25 mm or less.
  • the adhesion over time was measured as follows.
  • the test piece was created on the conditions similar to the prism sheet used for the measurement of adhesive force over time. After standing for 1 week in an atmosphere of 65 ° C. ⁇ 2 ° C. and a load of 6 kg / 400 cm 2 , 180 ° peel strength at 25 mm width was measured at a peel rate of 300 mm / min. .
  • the peeling force of the surface of the pressure-sensitive adhesive layer of the present invention and the surface of the base material layer opposite to the pressure-sensitive adhesive layer or the surface of the release layer is 10 cN / 25 mm or less at 23 ° C. It is preferable from the point of the delivery property of the film. If the peeling force exceeds 10 cN / 25 mm, problems occur such as partial elongation and deformation of the film when the protective film is in a roll form.
  • the peel strength at 23 ° C. is more preferably 5 cN / 25 mm or less, particularly preferably 3 cN / 25 mm or less.
  • the lower limit of the peel force to the surface of the adhesive layer of the protective film and the surface of the base material layer opposite to the surface of the adhesive layer or the surface of the release layer is about 1 cN / 25 mm or 2 cN / 25 mm as a practical value. Is preferred.
  • the adhesive composition and the polyolefin resin for the base layer, and if necessary, the polyolefin resin for the release layer are put into separate extruders and melted, Method of co-extrusion from T-die and laminating, or method of laminating other layers by lamination such as extrusion lamination and extrusion coating on layers obtained by inflation molding, film of each layer independently And the resulting films are laminated by dry lamination, etc., but from the viewpoint of productivity, the extruder of a multi-layered material for each of the release layer, the base layer, and the pressure-sensitive adhesive layer Co-extrusion molding to be supplied to molding is preferable, and in view of thickness accuracy, T-die molding is more preferable.
  • the protective film of the present invention is used to protect the surface of an adherend having a smooth or fine surface, and is particularly effective when the surface roughness is about 0.1 to 1.0 ⁇ m. It is.
  • Laminator Manufacturer Tester Industry Co., Ltd. Model: SA-1010-S Roll: Heat-resistant silicone rubber roll Roll diameter: 200 200
  • the test piece obtained is 23 ⁇ 2 ° C. and 50 ⁇ 5% relative humidity. H.
  • the sample was allowed to stand in the room for 30 minutes, and the 180 degree peel strength (unit: cN) in a width of 25 mm was measured under the conditions of peel speed 300 mm / min according to JIS Z0237 to obtain initial tack.
  • the surface protection film obtained is pasted under the same conditions as the prism sheet used in the initial tack evaluation of (1), 65 ° C ⁇ 2 ° C, After standing for 1 week in a 6 kg / 400 cm 2 atmosphere atmosphere, 23 ⁇ 2 ° C. and 50 ⁇ 5% relative humidity. H. It was left standing for 1 hour in the room. Subsequently, the film was peeled off by hand, and the presence or absence of adhesive residue on the back surface of the prism sheet was visually confirmed. Those with no adhesive residue or transferred material were rated as ((good), and those with even a small amount of adhesive residue or transferred material were rated as x (defect).
  • the surface roughness of the protective film obtained on the opposite side of the adhesive layer was evaluated using a three-dimensional roughness meter (Kosaka Laboratory, model number ET-30HK) with a stylus pressure of 20 mg. Measured in the X direction 1 mm, feed speed 100 ⁇ m / sec, feed pitch 2 ⁇ m in Y direction 99 recording lines, height magnification 20000 ⁇ , cut off 80 ⁇ m, JISB 0601 (1994) Calculated according to the definition of arithmetic mean roughness described. Arithmetic mean roughness (SRa) performed three trials each, and evaluated the average value.
  • SRa Arithmetic mean roughness
  • Block Copolymer of Block A The content of block A was calculated by comparing the spectrum of homo polystyrene with the infrared spectrum of each raw resin and the mixed resin sample.
  • Hydrogenation rate of double bond derived from conjugated diene monomer unit in polymer block B Hydrogenation rate of double bond derived from conjugated diene monomer unit in polymer block B is a polymer The content of the carbon-carbon double bond derived from the conjugated diene compound monomer unit in block B was measured by iodine value measurement, infrared spectrophotometer, 1 H-NMR spectrum and the like before and after hydrogenation. , It can be determined from the measured value.
  • EB-P trade name "EB-P", ethylenebisstearic acid amide, manufactured by Kao Corporation
  • Example 1 A PSA composition comprising 70 parts by weight of S1606, 5 parts by weight of TH130 and 20 parts by weight of ENDEX 155, and a polyolefin resin (trade name “WF 836 DG3”, propylene ethylene random copolymer, Prime Polymer Co., Ltd.
  • a polyolefin resin trade name “WF 836 DG3”, propylene ethylene random copolymer, Prime Polymer Co., Ltd.
  • the resin of the adhesive layer has a discharge rate of 4 kg / hour with a 40 mm ⁇ single-screw extruder
  • the resin of the base layer has a single 90 mm ⁇
  • the resin of the mold release layer is a 3-layer T-die with a discharge amount of 4 kg / h with a 60 mm single screw extruder at a discharge amount of 32 kg / h with a shaft extruder.
  • Example 2 to 5 Comparative Examples 1 to 8
  • a protective film was obtained in the same manner as in Example 1, except that the contents of the raw material resin and additives of the adhesive layer, and the thickness and content of the adhesive layer were changed as shown in Table 1. The above results are shown in Table 1.
  • the protective films of Examples 1 to 5 have sufficient adhesive strength when attached to the back surface of the prism sheet, and the adhesive strength is unlikely to develop even after one week at high temperature, and the peel strength is also reduced. It was suppressed and excellent. Moreover, the peeling force of the adhesive layer of a film and the surface on the opposite side was large, and the film was hard to be extended or deformed.
  • the protective film of Comparative Example 2 had weak initial adhesion to the prism back surface and was easily peeled off. In addition, the time-dependent adhesive strength was greatly increased compared to the initial adhesive strength.
  • the protective film of Comparative Example 3 had too strong adhesivity with time to the prism back surface, and was difficult to peel off. Moreover, the peeling force of the adhesive layer of a film and the surface on the opposite side was large, and the film was partially extended or deformed.
  • the protective film of Comparative Example 4 had too high initial tack and tack with time on the prism back surface, and was difficult to peel off. Moreover, the peeling force of the adhesive layer of a film and the surface on the opposite side was large, and the film was partially extended or deformed.
  • the protective film of Comparative Example 5 had very high initial tackiness to the prism back surface and tackiness with time, and was hard to peel off.
  • the protective film of Comparative Example 6 had a very high time-dependent adhesion to the prism back surface and was difficult to peel off.
  • the protective film of Comparative Example 7 had weak initial adhesion to the prism back surface and was easily peeled off.
  • the protective film of Comparative Example 8 had a large initial tack to the prism back surface and was hard to peel off. Moreover, the peeling force of the adhesive layer of a film and the surface on the opposite side was large, and it was a thing which a film extends partially or it is easy to deform
  • the pressure-sensitive adhesive composition of the present invention is industrially useful where the surface protective film of the present invention is suitably used for surface protection such as a prism sheet, particularly for the back surface thereof.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Inorganic Chemistry (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention fournit une composition d'adhésif qui, dans le cas d'un collage sur un support dont la surface présente de fines irrégularités, présente une force d'adhésion suffisante, laquelle force d'adhésion est peu susceptible d'augmenter y compris dans le cas d'une exposition à des températures élevées pendant son transport, son stockage, ou similaire. Plus précisément, l'invention concerne une composition de résine adhésive qui comprend une résine à base d'alpha-méthylstyrolène et une résine à base de terpène, et qui a pour composant principal un copolymère séquencé satisfaisant les points 1) et 2) suivants. 1) Être un copolymère séquencé contenant une séquence polymère (A) et une séquence polymère (B), et possédant une formule structurelle A-B-A et/ou une formule structurelle A-B. Séquence polymère (A) : séquence polymère configurant une unité dérivée d'une unité monomère de composé alcényle aromatique en tant qu'unité de répétition principale, et essentiellement constituée d'une unité dérivée d'une unité monomère de composé alcényle aromatique. Séquence polymère (B) : séquence copolymère de monomère d'alcényle aromatique et de monomère de diène conjugué comprenant de manière aléatoire une unité monomère de diène conjugué et une unité dérivée d'unité monomère de composé alcényle aromatique. 2) Présenter un taux d'hydrogénation d'une double liaison dérivée de ladite unité monomère de diène conjugué contenue dans ladite séquence polymère (B) supérieure ou égale à 90% en moles.
PCT/JP2018/031074 2017-09-04 2018-08-23 Composition de résine adhésive, et film protecteur mettant en œuvre celle-ci WO2019044637A1 (fr)

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CN111051460B (zh) 2022-03-11
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CN111051460A (zh) 2020-04-21
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