WO2016163153A1 - Composition adhésive photodurcissable - Google Patents

Composition adhésive photodurcissable Download PDF

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Publication number
WO2016163153A1
WO2016163153A1 PCT/JP2016/054272 JP2016054272W WO2016163153A1 WO 2016163153 A1 WO2016163153 A1 WO 2016163153A1 JP 2016054272 W JP2016054272 W JP 2016054272W WO 2016163153 A1 WO2016163153 A1 WO 2016163153A1
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WO
WIPO (PCT)
Prior art keywords
meth
adhesive composition
photocurable adhesive
acrylate
hydrogenated
Prior art date
Application number
PCT/JP2016/054272
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English (en)
Japanese (ja)
Inventor
聖 金子
智仁 寺田
Original Assignee
協立化学産業株式会社
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Filing date
Publication date
Application filed by 協立化学産業株式会社 filed Critical 協立化学産業株式会社
Priority to CN201680019363.7A priority Critical patent/CN107429123B/zh
Priority to KR1020177027926A priority patent/KR102246492B1/ko
Publication of WO2016163153A1 publication Critical patent/WO2016163153A1/fr

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Classifications

    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/08—Homopolymers or copolymers of acrylic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • 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
    • C09J11/08—Macromolecular additives
    • 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
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/10—Homopolymers or copolymers of methacrylic acid esters
    • 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
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/416—Additional features of adhesives in the form of films or foils characterized by the presence of essential components use of irradiation

Definitions

  • the present invention relates to a photocurable adhesive composition, a laminate using the same, an optical display using the same, and a method for manufacturing the laminate.
  • a display body such as a liquid crystal display panel or an organic EL panel is directly bonded to a touch panel or a display body and a protection for reinforcement from the viewpoint of preventing visibility deterioration due to surface reflection.
  • a front plate such as a panel or a touch panel and a front plate are bonded together.
  • Patent Document 2 irradiates a photocurable resin composition containing polyisoprene methacrylate oligomer, dicyclopentenyloxyethyl methacrylate and lauryl methacrylate with ultraviolet rays under reduced pressure or in an inert gas atmosphere such as nitrogen. A method is disclosed.
  • Patent Document 2 it is necessary to introduce a device for providing a reduced pressure or an inert gas atmosphere in order to exclude the influence of the inhibition of curing by oxygen.
  • the present invention provides a photocurable adhesive composition that solves the above-described problems and provides a laminate having an adhesive strength equivalent to that in the absence of oxygen even when irradiated with light in the presence of oxygen. With the goal.
  • the present invention has the following configuration.
  • (D) A photocurable adhesive composition comprising a tackifier having a softening point of 70 to 150 ° C. and
  • E a liquid plasticizer.
  • the component (A) is at least one selected from the group consisting of (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, and a (meth) acrylate oligomer having a polyurethane structure in the skeleton.
  • Photocurable adhesive composition [3] The photocurable adhesive composition according to [1] or [2], wherein the component (B) is at least one selected from the group consisting of alkyl (meth) acrylates and hydroxy-substituted alkyl (meth) acrylates. [4] A laminate bonded with the photocurable adhesive composition according to any one of [1] to [3]. [5] The laminate according to [4], which is an optical display.
  • a method for producing a laminate comprising the following steps (I) to (III): (I) a step of applying a photocurable adhesive composition according to any one of [1] to [3] to the substrate 1 to form a photocurable adhesive composition layer; (II) A step of irradiating the photocurable adhesive composition layer obtained in step (I) with energy rays to form a cured product of the photocurable adhesive composition, and (III) obtained in step (II).
  • the manufacturing method including the process of bonding the base material 2 on the obtained hardened
  • a photocurable adhesive composition that provides a laminate having an adhesive strength equivalent to that in the absence of oxygen even when irradiated with light in the presence of oxygen.
  • the photocurable adhesive composition has (A) a tetrafunctional or higher (meth) acrylate oligomer having a molecular weight of 10,000 to 70,000, (B) a monofunctional (meth) acrylate monomer, and (C) initiation of photoreaction. Agent, (D) a tackifier having a softening point of 70 to 150 ° C., and (E) a liquid plasticizer.
  • (A) A tetrafunctional or higher functional (meth) acrylate oligomer (hereinafter also referred to as “(A) oligomer”) having a molecular weight of 10,000 to 70,000 has four or more (meth) acryloyl groups in the molecule.
  • (meth) acrylate” includes both “acrylate” and “methacrylate”.
  • the “(meth) acryloyl group” includes both “acryloyl group” and “methacryloyl group”.
  • the molecular weight of the oligomer is 10,000 to 70,000, more preferably 20,000 to 50,000. If the molecular weight of the oligomer is less than 10,000, the elastic modulus increases and flexibility tends to decrease. If the molecular weight of the oligomer exceeds 70,000, the viscosity increases and workability decreases. Tend. In the present specification, the molecular weight is a weight average molecular weight measured by gel permeation chromatography (GPC) and converted using a standard polystyrene calibration curve.
  • GPC gel permeation chromatography
  • the functional number of the oligomer (the number of (meth) acryloyl groups) is 4 or more, preferably 4 to 10 functions, more preferably 4 to 6 functions, and particularly preferably 4 functions.
  • the oligomer functional number is 3 or less, when light is irradiated in the presence of oxygen, the inhibition of curing by oxygen becomes remarkable, and the adhesive strength decreases.
  • the functional number of the oligomer (A) is 10 or less, the adhesive strength does not decrease when light irradiation is performed in the presence of oxygen, and an increase in elastic modulus accompanying an increase in the functional number is suppressed.
  • the oligomer is not particularly limited, and examples thereof include (hydrogenated) polyisoprene, (hydrogenated) polybutadiene, and (meth) acrylate oligomers having a polyurethane as a skeleton. These (meth) acrylate oligomers can be used alone or in combination of two or more.
  • (hydrogenated) polyisoprene includes polyisoprene and / or hydrogenated polyisoprene
  • (hydrogenated) polybutadiene includes polybutadiene and / or hydrogenated polybutadiene.
  • Polybutadiene (meth) acrylate oligomer having a skeleton includes (hydrogenated) polybutadiene (meth) acrylate and (hydrogenated) polybutadiene urethane (meth) acrylate.
  • Polyisoprene-containing (meth) acrylate oligomers include (hydrogenated) polyisoprene (meth) acrylate and (hydrogenated) polyisoprene urethane (meth) acrylate.
  • Examples of the (meth) acrylate oligomer having a polyurethane as a skeleton include a polyether-based, polycarbonate-based, polyester-based, or a combination thereof.
  • a commercially available product of the oligomer (A) having a polyurethane as a skeleton UV-7610B (manufactured by Nippon Synthetic Chemical Co., Ltd .; molecular weight 11,000, 9 functions) and the like can be mentioned.
  • the oligomer preferably has (hydrogenated) polybutadiene as a skeleton, and more preferably urethane (meth) acryl-modified (hydrogenated) polybutadiene.
  • the oligomer may be used alone or in combination of two or more.
  • the oligomer (A) can be produced, for example, by the method described in JP 2014-189758 A or JP 2002-309185 A. Moreover, (A) oligomer can be manufactured by the method of condensing hydroxyl-containing resin and (meth) acrylic acid, and the method of transesterifying (meth) acrylic acid ester and hydroxyl-containing resin. Furthermore, (A) the oligomer is specifically selected from the group consisting of hydroxyl group-containing (hydrogenated) polybutadiene, hydroxyl group-containing (hydrogenated) polyisoprene, hydroxyl group-containing polyester, hydroxyl group-containing polyether, and hydroxyl group-containing polycarbonate.
  • the hydroxyl group-containing resin, polyisocyanate, hydroxyl group-containing (meth) acrylate and (meth) acrylic acid ester will be described.
  • the hydroxyl group-containing resin is a raw material resin of (meth) acrylate oligomer, and examples thereof include hydroxyl group-containing (hydrogenated) polybutadiene, hydroxyl group-containing (hydrogenated) polyisoprene, hydroxyl group-containing polyester, hydroxyl group-containing polyether, and hydroxyl group-containing polycarbonate.
  • Hydroxyl group-containing resins are polybutadiene having hydroxyl groups at both ends (hydrogenated), polyisoprene having hydroxyl groups at both ends (hydrogenated), polyester having hydroxyl groups at both ends, polyether having hydroxyl groups at both ends, and both A polycarbonate having a hydroxyl group at the end is preferred.
  • one or more (meth) acryloyl groups, preferably two or more (meth) acryloyl groups can be introduced at both ends.
  • Polybutadienes having hydroxyl groups at both ends include GI-3000 (manufactured by Nippon Soda Co., Ltd.), GI-1000 (manufactured by Nippon Soda Co., Ltd.), G-3000 (manufactured by Nippon Soda Co., Ltd.), Poly bd (Idemitsu Kosan Co., Ltd.) Manufactured) and the like.
  • Examples of polyisoprene having hydroxyl groups at both ends (hydrogenated) include Poly ip (manufactured by Idemitsu Kosan Co., Ltd.).
  • Polyesters having hydroxyl groups at both ends, polyethers having hydroxyl groups at both ends, and polycarbonates having hydroxyl groups at both ends include Polylite OD-X-2251 (manufactured by DIC), PPG (manufactured by Mitsui Chemicals), Duranol. T5652 (manufactured by Asahi Kasei Chemical Co., Ltd.), Preminol 4004, Preminol 4015 (manufactured by Asahi Glass Co., Ltd.), Adeka Polyether P-3000, Adeka New Ace V14-90 (manufactured by Adeka Co., Ltd.), etc. It can be used according to the molecular weight and polarity, and is not particularly limited.
  • the polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanato groups, and examples thereof include aromatic, aliphatic, and alicyclic polyisocyanates.
  • aromatic polyisocyanate examples include tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, phenylene diisocyanate, and naphthalene diisocyanate.
  • alicyclic polyisocyanate examples include hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, norbornene diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and the like.
  • aliphatic polyisocyanate examples include hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, and lysine triisocyanate.
  • the hydroxyl group-containing (meth) acrylate is not particularly limited as long as it is a (meth) acrylate compound having one or more hydroxyl groups and one or more (meth) acryloyl groups in the molecule.
  • Hydroxyl group-containing (meth) acrylates include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2- (meth) acryloyl It has one hydroxyl group and one (meth) acryloyl group in a molecule such as oxyethyl-2-hydroxypropyl phthalate, caprolactone-modified 2-hydroxyethyl (meth) acrylate, cyclohexanedimethanol mono (meth) acrylate (meta ) Acrylate; 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, etc., one hydroxyl group in the molecule Beauty having two or more (meth) acrylo
  • the oligomer (A) can be obtained by adjusting the number of hydroxyl groups in the hydroxyl group-containing resin and the number of (meth) acryloyl groups in the hydroxyl group-containing (meth) acrylate.
  • the combination of the hydroxyl group-containing resin and the hydroxyl group-containing (meth) acrylate is not particularly limited as long as the resulting oligomer has 4 or more (meth) acryloyl groups in the molecule.
  • the hydroxyl group-containing resin is a resin having one hydroxyl group at both ends, and the hydroxyl group-containing (meth) acrylate has one hydroxyl group and one or more hydroxyl groups.
  • a combination of a hydroxyl group-containing resin and a hydroxyl group-containing (meth) acrylate, which is a (meth) acrylate compound having a (meth) acryloyl group, may be mentioned.
  • the (meth) acrylic acid ester is not particularly limited as long as it is a (meth) acrylate compound having one or more (meth) acryloyl groups in the molecule and no hydroxyl group.
  • Examples of such compounds include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, (Meth) acrylic acid alkyl esters such as stearyl (meth) acrylate and isostearyl (meth) acrylate; aralkyl esters of (meth) acrylic acid such as benzyl (meth) acrylate; cyclohexyl (meth) acrylate and isobornyl (meth) acrylate And alicyclic esters of (meth) acrylic acid such as dicyclopentanyl (meth) acrylate; heterocyclyl esters of (meth) acrylic acid such as tetrahydrofurfuryl (meth) acrylate
  • the conditions such as the amount of each component used, the reaction temperature, and the reaction time are not particularly limited as long as (A) the oligomer can be obtained, and can be appropriately selected.
  • the (B) monofunctional (meth) acrylate monomer is not particularly limited as long as it is a (meth) acrylate compound having one (meth) acryloyl group in the molecule.
  • Monofunctional (meth) acrylate monomers include 2-ethylhexyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, isodecyl (meth) acrylate, Alkyl (meth) acrylates such as lauryl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate; alkoxy-substituted alkyl (meth) acrylates such as methoxyethyl (meth) acrylate; 2-hydroxyethyl (meth) acrylate Hydroxy-substituted alkyl (meth) acrylates such as 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like; Hydroxy-substituted al
  • the (B) monofunctional (meth) acrylate monomer is preferably at least one selected from the group consisting of alkyl (meth) acrylates and hydroxy-substituted alkyl (meth) acrylates.
  • the monofunctional (meth) acrylate monomer may be used alone or in combination of two or more.
  • two or more (B) monofunctional (meth) acrylate monomers are used in combination, a combination of an alkyl (meth) acrylate and a hydroxy-substituted alkyl (meth) acrylate is preferred.
  • the (B) monofunctional (meth) acrylate monomer is preferably 1 to 250 parts by mass, more preferably 20 to 200 parts by mass, and even more preferably 30 to 30 parts by mass with respect to 100 parts by mass of the (A) oligomer. 150 parts by mass, particularly preferably 40 to 90 parts by mass.
  • the photoinitiator is not particularly limited, and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 1-hydroxy-cyclohexyl- Phenyl-ketone, benzophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide, 2- Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1,2-hydroxy-2-methyl-1-phenyl-propan-1-one, 2-methyl-1- [4-methylthio] phenyl] -2-morpholinopropan-1-one, benzoin methyl ether, benzoin ethyl ether, ben Inisobutyl ether, benzoin isopropyl ether,
  • the photoinitiator is preferably one or more selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone and 2,4,6-trimethylbenzoylphenylethoxyphosphine oxide.
  • the photoinitiator may be used alone or in combination of two or more.
  • the photoreaction initiator is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 15 parts by mass, and still more preferably 1 to 100 parts by mass of the (A) oligomer. ⁇ 10 parts by mass.
  • the photocurable adhesive composition contains (D) a tackifier having a softening point of 70 to 150 ° C. (hereinafter also referred to as “(D) tackifier”).
  • (D) tackifier a tackifier having a softening point of 70 to 150 ° C.
  • the photocurable adhesive composition contains (D) a tackifier, the adhesive strength can be improved, the cured product can be softened, and the followability to the adherend can be improved.
  • the softening point of the tackifier is preferably 75 to 130 ° C., more preferably 80 to 120 ° C., from the viewpoint of adhesive strength and flexibility.
  • the softening point is a value measured by the ring and ball method.
  • the tackifier is not particularly limited as long as the above softening point is satisfied, and rosin ester-based resins such as disproportionated rosin ester, polymerized rosin ester, (hydrogenated) rosin ester; acrylic polymer, acrylic copolymer, etc.
  • the tackifier is preferably a rosin ester resin and more preferably a hydrogenated rosin ester.
  • the rosin ester resin since the carboxylic acid portion of the rosin is esterified, the influence of the acid component on the adherend (for example, the wiring portion of the touch panel) can be suppressed.
  • the hydrogenated rosin ester can also prevent coloring when exposed to initial and heat because the rosin is hydrogenated.
  • the tackifier may be used alone or in combination of two or more.
  • the amount of the tackifier can be 5 to 70% by mass in 100% by mass of the photocurable adhesive composition. If it is this range, the quantity of a reaction component is appropriate, and while favorable film property is obtained, it is advantageous also in the expression effect of adhesive strength.
  • the tackifier is preferably 10 to 60% by mass, more preferably 15 to 50% by mass in 100% by mass of the photocurable adhesive composition.
  • the photocurable adhesive composition contains (E) a liquid plasticizer.
  • “Liquid” refers to fluidity at 25 ° C. under atmospheric pressure. For example, a viscosity of 1,000 Pa ⁇ s or less (for example, a viscosity of 0.01 to 1,000 Pa ⁇ s) with a cone plate viscometer. To show.
  • the photocurable adhesive composition contains (E) a liquid plasticizer, a flexible cured product having a low elastic modulus can be obtained.
  • liquid plasticizers include phthalates such as dibutyl phthalate, diisononyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, diisodecyl phthalate, butyl benzyl phthalate; dioctyl adipate, diisononyl adipate, dioctyl sebacate Polycarboxylic acid alkyl esters such as diisononyl sebacate and diisononyl 1,2-cyclohexanedicarboxylate (for example, C3 to C12 alkyl esters of polycarboxylic acid); phosphate esters such as tricresyl phosphate and tributyl phosphate; Trimellitic acid esters; alkyl esters of polyoxyalkylene glycols such as triethylene glycol bis (2-ethylhexanoate) (eg, di-, tri- or tetra),
  • thermoplastic elastomers such as terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins; Rosin resins; disproportionated rosin ester resins, polymerized rosin ester resins, (hydrogenated) rosin ester resins such as rosin ester resins; xylene resins; acrylic resins such as acrylic polymers and acrylic copolymers .
  • terpene resins such as terpene resins, terpene phenol resins, modified terpene resins, hydrogenated terpene resins
  • Rosin resins disproportionated rosin ester resins, polymerized rosin ester resins, (hydrogenated) rosin ester resins such as rosin ester resins
  • xylene resins such as acrylic polymers and acrylic copolymers .
  • the liquid plasticizer is preferably a rosin ester resin (provided that it is liquid), and is preferably a hydrogenated rosin ester (provided that it is liquid).
  • a liquid plasticizer may be used alone or in combination of two or more.
  • the liquid plasticizer can be used in an amount of 300 parts by mass or less with respect to 100 parts by mass of the (D) tackifier, from the viewpoint of the development of strength by the (D) tackifier. From the viewpoint of adhesive strength and flexibility, the content is preferably 10 to 250 parts by mass, more preferably 30 to 200 parts by mass, and still more preferably 50 to 150 parts by mass.
  • the adhesion-imparting agent, antioxidant, antifoaming agent, pigment, filler, chain transfer agent, light stabilizer, surface tension modifier, and leveling are within the range not impairing the effects of the present invention.
  • An agent, an ultraviolet absorber, an antifoaming agent, etc. can be blended.
  • Further components may be used alone or in combination of two or more. The total content of further components is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, and still more preferably 1 to 100 parts by mass of the oligomer (A). Is 5 parts by mass.
  • the photocurable adhesive composition can be prepared by mixing each component.
  • the mixing method is not particularly limited, and various metals, plastic containers, stirring blades, and a stirrer can be used.
  • the photocurable adhesive composition can be used for bonding any base material 1 and any base material 2 together.
  • the substrate 1 and the substrate 2 may be the same substrate or different substrates.
  • At least one of the substrate 1 and the substrate 2 can be a light transmissive member.
  • the cured resin layer can be formed by irradiating the photocurable adhesive composition with energy rays (for example, ultraviolet rays) from the light transmissive member side.
  • the light transmissive member include glass, (meth) acrylic resin, polyethylene terephthalate, polyethylene naphthalate, polycarbonate, polyimide, polyester, and cycloolefin polymer.
  • the photocurable adhesive composition is preferably for bonding the display body and the touch panel, the display body and the front plate, or the touch panel and the front plate.
  • An optical display body is obtained by bonding a display body and a touch panel, a display body and a front plate, or a touch panel and a front plate using a photocurable adhesive composition.
  • the front plate examples include glass or engineering plastic, for example, an acrylic plate (which may be subjected to a single-sided or double-sided hard coat treatment or AR coat treatment), a transparent plastic plate such as a polycarbonate plate, a PET plate, or a PEN plate.
  • the front plate can also be a protective panel.
  • the touch panel examples include a resistive film type, a capacitance type, an electromagnetic induction type, and an optical type touch panel.
  • the display examples include LCD, EL display, EL illumination, electronic paper, and plasma display.
  • the front plate, the touch panel, and the display body may have a step or have a light shielding portion.
  • the light-shielding part refers to a part where the photocurable adhesive composition applied to the adhesive surface is not exposed to energy rays (for example, ultraviolet rays) necessary for curing.
  • the laminated body obtained by bonding together with a photocurable adhesive composition is also an object of the present invention.
  • a laminated body is obtained by bonding arbitrary base materials 1 and arbitrary base materials 2 with a photocurable adhesive composition.
  • the manufacturing method of a laminated body is not specifically limited, It is preferable that it is the manufacturing method of the laminated body mentioned later.
  • the laminated body obtained by bonding together with a photocurable adhesive composition is an optical display body.
  • the method for producing a laminate is a method for producing a laminate in which a substrate 1 and a substrate 2 are laminated via a cured product of a photocurable adhesive composition, and the following steps (I) to (III) ): (I) a step of applying a photocurable adhesive composition to the substrate 1 to form a photocurable adhesive composition layer; (II) A step of irradiating the photocurable adhesive composition layer obtained in step (I) with energy rays to form a cured product of the photocurable adhesive composition, and (III) obtained in step (II). A step of bonding the base material 2 on the cured product thus obtained is included.
  • the photocurable adhesive composition, the substrate 1 and the substrate 2 include the preferred embodiments and are as described above. Therefore, it is preferable that the manufacturing method of a laminated body is a manufacturing method of an optical display body. Moreover, it is preferable that the laminated body obtained by the manufacturing method of a laminated body is an optical display body.
  • Step (I) is a step of applying a photocurable adhesive composition to the substrate 1 to form a photocurable adhesive composition layer.
  • the method for applying the photocurable adhesive composition to the substrate 1 is not particularly limited, and a method using a die coater, a dispenser, screen printing, or the like can be used.
  • the thickness of the photocurable adhesive composition layer is not particularly limited, and can be, for example, 10 to 500 ⁇ m, and preferably 30 to 350 ⁇ m.
  • Step (II) is a step of irradiating the photocurable adhesive composition layer obtained in step (I) with energy rays to form a cured product of the photocurable adhesive composition.
  • Energy rays are not particularly limited, and active energy rays such as visible light, ultraviolet rays, X-rays, and electron beams can be used.
  • the energy ray is preferably ultraviolet light.
  • a light source that emits ultraviolet light (UV) can be used.
  • the ultraviolet light source include a metal halide lamp, a high-pressure mercury lamp, a xenon lamp, a mercury xenon lamp, a halogen lamp, a pulse xenon lamp, and an LED.
  • the peak wavelength of the LED is not particularly limited, and examples thereof include 365 nm, 405 nm, 375 nm, 385 nm, and 395 nm.
  • Light emitted from a light source other than the LED may be adjusted to light of a specific wavelength by passing through an optical filter. Specifically, it can be adjusted by passing through an optical filter that cuts light having a wavelength of 300 nm or less and / or an optical filter that cuts light having a wavelength of 500 nm or more.
  • the energy rays can be irradiated so that the integrated light quantity of the energy rays is 30 to 15,000 mJ / cm 2 .
  • the integrated light quantity is preferably 50 to 12,000 mJ / cm 2 , and more preferably 100 to 10,000 mJ / cm 2 .
  • the cured resin layer can be formed by irradiating energy rays from the photocurable adhesive composition side.
  • the energy ray may be applied to the light curable adhesive composition from the light transmissive member side to form a cured resin layer.
  • reaction rate of the photocurable adhesive composition in the cured product formed in step (II) is not particularly limited, it is preferably 90% or more. When the reaction rate is 90% or more, sufficient strength is exhibited without further irradiation after bonding, and thus the process can be simplified. In addition, there is no concern about penetration and damage to other members due to the photocurable adhesive composition remaining uncured, bleeding out from the cured product, and a light shielding layer that does not transmit light is provided in the laminate. It can also be applied to bonding of substrates that do not transmit light at all.
  • the reaction rate is defined by the reduction rate of (meth) acryloyl groups in the photocurable adhesive composition before and after irradiation with energy rays (for example, ultraviolet rays), and can be measured by FT-IR.
  • energy rays for example, ultraviolet rays
  • the case where all the (meth) acryloyl groups in a photocurable adhesive composition reacted is set to 100%.
  • Step (III) is a step in which the substrate 2 is bonded onto the cured product obtained in step (II) to obtain a laminate.
  • the substrate 2 can be placed on the substrate 1 on which the cured product is formed so as to be in contact with the cured product, and the substrate 1 and the substrate 2 can be bonded to each other.
  • the base material 2 is a base material to which the photocurable adhesive composition was not applied in the step (I).
  • the manufacturing method of a laminated body may include the process of pressurizing the bonding body which consists of the base material 1, the base material 2, and the hardened
  • the adhesive strength of a laminated body improves more because the manufacturing method of a laminated body includes a pressurization process.
  • the pressure treatment can be performed using a rubber roller, a flat plate press device or the like.
  • Synthesis Example 1 (Production of polybutadiene urethane acrylate A) A four-necked flask equipped with a thermometer, a stirrer, a dropping funnel, and a cooling tube with a drying tube was charged with a hydroxylated hydrogenated polybutadiene (GI-3000, manufactured by Nippon Soda Co., Ltd., number average molecular weight 3,000, iodine value 21).
  • GI-3000 manufactured by Nippon Soda Co., Ltd., number average molecular weight 3,000, iodine value 21.
  • Synthesis Example 2 (Production of polybutadiene urethane acrylate B) A polyurethane acrylate oligomer having an average functional group number of 2 and a weight average molecular weight of 26,000 was obtained in the same manner as in Synthesis Example 1 except that the amount of isophorone diisocyanate was changed to 26.7 g (0.120 mol).
  • Synthesis Example 3 (Production of polybutadiene urethane acrylate C) A polyurethane acrylate oligomer having an average functional group number of 2 and a weight average molecular weight of 43,000 was obtained in the same manner as in Synthesis Example 1 except that the amount of isophorone diisocyanate was changed to 23.1 g (0.104 mol).
  • Synthesis Example 4 (Production of polybutadiene urethane acrylate D) The same procedure as in Synthesis Example 2, except that 17.1-g (0.080 mol) of 2-hydroxy-3-acryloyloxypropyl methacrylate (NK ester 701A, Shin-Nakamura Chemical Co., Ltd.) was used instead of 4-hydroxybutyl acrylate.
  • Synthesis Example 5 (Production of polybutadiene urethane acrylate E) A polyurethane acrylate oligomer having an average functional group number of 4 and a weight average molecular weight of 36,000 was obtained in the same manner as in Synthesis Example 4 except that the amount of isophorone diisocyanate was changed to 24.9 g (0.112 mol).
  • Synthesis Example 6 (Production of polybutadiene urethane acrylate F) A polyurethane acrylate oligomer having an average functional group number of 4 and a weight average molecular weight of 42,000 was obtained in the same manner as in Synthesis Example 4 except that the amount of isophorone diisocyanate was changed to 23.1 g (0.104 mol).
  • the elastic modulus conforms to JISZ1702 and is No.
  • Three dumbbell test pieces (thickness 1 mmt) were prepared, and measured at a speed of 10 mm / min using a tensile / compression tester (manufactured by Minebea, Technograph TG-2kN).
  • the dumbbell specimen a conveyor-type metal halide lamp (manufactured by Eye Graphics Co., 200 mW / cm 2) was used to a photocurable adhesive composition prepared from a cured product obtained by curing at 6,000 mJ / cm 2.
  • Test specimens for OPEN strength and CLOSE strength were obtained as follows.
  • ⁇ Opening Curing Strength Test Piece A spacer with a thickness of 150 ⁇ mt prepared using three cellophane tapes (50 ⁇ mt) on the base material 1 (26 mm ⁇ 75 mm ⁇ 1.1 mmt, glass) so that the coated portion of the photocurable adhesive composition has a width of 20 mm.
  • a conveyor-type metal halide lamp made by Eye Graphics, 200 mW / cm 2
  • Light was irradiated from the photocurable adhesive composition layer side at 3,000 mJ / cm 2 to form a cured product of the photocurable adhesive composition.
  • the base material 3 (26 mm ⁇ 150 mm ⁇ 0.1 mmt, PET) was placed on the cured product of the photocurable adhesive composition and bonded to obtain an OPEN cured strength measurement test piece.
  • ⁇ CLOSE Strength Test Specimen A spacer with a thickness of 150 ⁇ mt prepared using three cellophane tapes (50 ⁇ mt) on the base material 1 (26 mm ⁇ 75 mm ⁇ 1.1 mmt, glass) so that the coated portion of the photocurable adhesive composition has a width of 20 mm. Is applied, a photocurable adhesive composition is applied using a metal squeegee to form a photocurable adhesive composition layer, and then the substrate 2 (26 mm ⁇ 75 mm ⁇ 0.05 mmt, release PET) is photocured.
  • OPEN intensity and CLOSE intensity were measured at a speed of 300 mm / min using a tensile / compression tester (manufactured by Minebea, Technograph TG-2kN).
  • ⁇ Intensity change rate> The intensity change rates of the above OPEN intensity and CLOSE intensity were determined. The case where the intensity change rate was 20% or less was evaluated as “ ⁇ ”, and the case where it was over 20% was evaluated as “X”.
  • the reaction rate of the photocurable adhesive composition in the cured product of the photocurable adhesive composition is FT-IR (Speckin 100, manufactured by Perkin Elmer Co., Ltd.) as a reduction rate of the acryloyl group before and after the energy ray irradiation of the photocurable adhesive composition. ).
  • the rate of decrease is the absorption peak height (X) of 800 to 820 cm ⁇ 1 from the base line in the FT-IR measurement chart of the photocurable adhesive composition layer before irradiation with energy rays, and the photocurable adhesive after irradiation with energy rays.
  • the base material 3 (26 mm ⁇ 150 mm ⁇ 0.1 mmt, PET) was placed on the cured product of the photocurable adhesive composition and bonded to obtain an OPEN cured strength measurement test piece.
  • the reaction rate of the photocurable adhesive composition was measured for the cured product of the photocurable adhesive composition in the OPEN cured strength test specimen.
  • a spacer with a thickness of 150 ⁇ mt prepared using three cellophane tapes (50 ⁇ mt) on the base material 1 (26 mm ⁇ 75 mm ⁇ 1.1 mmt, glass) so that the coated portion of the photocurable adhesive composition has a width of 20 mm. Is applied, a photocurable adhesive composition is applied using a metal squeegee to form a photocurable adhesive composition layer, and then the substrate 2 (26 mm ⁇ 75 mm ⁇ 0.05 mmt, release PET) is photocured.
  • Example 1 to 3 the rate of change in strength was 0 (that is, there was no difference in strength between OPEN curing and CLOSE curing). That is, by including a tetrafunctional or higher (meth) acrylate oligomer, even when irradiated with light in the presence of oxygen, the adhesive strength was the same as when no oxygen was present.
  • Comparative Examples 1 to 3 do not contain a (meth) acrylate oligomer having 4 or more functional groups, so that the adhesive strength when irradiated with light in the presence of oxygen is compared to the adhesive strength when irradiated with light when oxygen is not present. The strength decreased.
  • the photocurable adhesive composition is useful as a laminate, particularly an optical display and an adhesive for the optical display.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne une composition adhésive photodurcissable qui permet d'obtenir un stratifié ayant la même force adhésive quand il est exposé à la lumière en présence d'oxygène que quand il est exposé à la lumière en l'absence d'oxygène, ladite composition contenant : (A) un oligomère de (méth)acrylate ayant au moins quatre groupes fonctionnels et un poids moléculaire de 10 000 à 70 000; (B) un monomère de (méth)acrylate monofonctionnel; (C) un initiateur de photoréaction; (D) un tackifiant ayant un point de ramollissement de 70 à 150°C; et (E) un plastifiant liquide.
PCT/JP2016/054272 2015-04-09 2016-02-15 Composition adhésive photodurcissable WO2016163153A1 (fr)

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