WO2022092199A1 - 粘着テープ - Google Patents

粘着テープ Download PDF

Info

Publication number: WO2022092199A1
Authority: WO; WIPO (PCT)
Prior art keywords: base material; weight; layer; material layer; adhesive tape
Prior art date: 2020-10-28

Application number

PCT/JP2021/039819

Other languages

English (en)

French (fr)

Japanese (ja)

Inventor

明史堀尾

泰志石堂

誠福山

妃那安田

達哉西垣

Original Assignee

積水化学工業株式会社

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

2020-10-28

Filing date

2021-10-28

Publication date

2022-05-05

2021-10-28 Application filed by 積水化学工業株式会社 filed Critical 積水化学工業株式会社

2021-10-28 Priority to CN202180070684.0A priority Critical patent/CN116367994A/zh

2021-10-28 Priority to JP2022507396A priority patent/JPWO2022092199A1/ja

2021-10-28 Priority to KR1020237000291A priority patent/KR20230093413A/ko

2022-05-05 Publication of WO2022092199A1 publication Critical patent/WO2022092199A1/ja

Links

239000002390 adhesive tape Substances 0.000 title claims abstract description 83
229920005989 resin Polymers 0.000 claims abstract description 73
239000011347 resin Substances 0.000 claims abstract description 73
238000005259 measurement Methods 0.000 claims abstract description 37
238000003860 storage Methods 0.000 claims abstract description 30
239000000853 adhesive Substances 0.000 claims abstract description 25
230000001070 adhesive effect Effects 0.000 claims abstract description 22
239000000758 substrate Substances 0.000 claims abstract description 15
239000010410 layer Substances 0.000 claims description 222
239000000463 material Substances 0.000 claims description 136
239000000178 monomer Substances 0.000 claims description 106
239000004820 Pressure-sensitive adhesive Substances 0.000 claims description 69
239000006260 foam Substances 0.000 claims description 49
NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 42
229920002554 vinyl polymer Polymers 0.000 claims description 23
229920001577 copolymer Polymers 0.000 claims description 21
239000012790 adhesive layer Substances 0.000 claims description 13
230000035939 shock Effects 0.000 abstract 1
XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 39
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238000000034 method Methods 0.000 description 30
239000003431 cross linking reagent Substances 0.000 description 26
239000000499 gel Substances 0.000 description 22
238000012360 testing method Methods 0.000 description 22
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239000000243 solution Substances 0.000 description 18
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125000000524 functional group Chemical group 0.000 description 15
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238000005187 foaming Methods 0.000 description 14
-1 2-ethylhexyl group Chemical group 0.000 description 12
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239000002184 metal Substances 0.000 description 10
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125000004432 carbon atom Chemical group C* 0.000 description 9
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239000004088 foaming agent Substances 0.000 description 7
239000002994 raw material Substances 0.000 description 7
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125000003700 epoxy group Chemical group 0.000 description 5
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239000003505 polymerization initiator Substances 0.000 description 4
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239000012987 RAFT agent Substances 0.000 description 3
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239000003963 antioxidant agent Substances 0.000 description 3
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229920000098 polyolefin Polymers 0.000 description 1
229920001296 polysiloxane Polymers 0.000 description 1
229920002223 polystyrene Polymers 0.000 description 1
238000010992 reflux Methods 0.000 description 1
230000003252 repetitive effect Effects 0.000 description 1
235000009566 rice Nutrition 0.000 description 1
229930195734 saturated hydrocarbon Natural products 0.000 description 1
FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical class [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 1
238000010898 silica gel chromatography Methods 0.000 description 1
229920002050 silicone resin Polymers 0.000 description 1
239000002356 single layer Substances 0.000 description 1
150000003384 small molecules Chemical class 0.000 description 1
HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical class O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
238000000638 solvent extraction Methods 0.000 description 1
125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
239000000126 substance Substances 0.000 description 1
125000003944 tolyl group Chemical group 0.000 description 1
LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
KEROTHRUZYBWCY-UHFFFAOYSA-N tridecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCOC(=O)C(C)=C KEROTHRUZYBWCY-UHFFFAOYSA-N 0.000 description 1

Classifications

- 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
- 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
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
- 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
- C09J7/26—Porous or cellular 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
- C09J7/20—Adhesives in the form of films or foils characterised by their carriers
- C09J7/29—Laminated material
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
- 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
- C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
- C09J2203/366—Applications of adhesives in processes or use of adhesives in the form of films or foils for mounting tapes
- 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
- C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
- C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
- C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape

Definitions

the present invention relates to an adhesive tape.
Adhesive tapes are used for assembly in mobile electronic devices such as mobile phones and personal digital assistants (PDAs) (for example, Patent Documents 1 and 2). Adhesive tapes are also used for fixing in-vehicle electronic device parts such as in-vehicle panels to the vehicle body.
PDAs personal digital assistants
Adhesive tapes used for fixing portable electronic device parts, in-vehicle electronic device parts, and the like are required to have high adhesive strength and impact resistance that does not peel off even when impacted.
portable electronic devices, in-vehicle electronic devices, etc. tend to have more complicated shapes due to higher functionality. be.
the adhesive tape is required to have excellent flexibility to follow the shape of the adherend.
an adhesive tape having excellent flexibility and impact resistance for example, an adhesive tape using a foam base material obtained by foaming a polyolefin resin or the like is known.
electronic devices have been required to withstand repeated impacts (continuous impacts) due to harsher and diversified usage conditions, and conventional adhesive tapes using a foam base material have been used. Even if it does not peel off with a single impact, there is a problem that it peels off or the adherend is damaged when an impact such as dropping is repeatedly applied.
An object of the present invention is to provide an adhesive tape having excellent repeated impact resistance.
the present invention is an adhesive tape having a multilayer base material and an adhesive layer laminated on at least one surface of the multilayer base material, wherein the multilayer base material is a base material layer and the base material layer.
the base material layer has a resin layer laminated on at least one surface, and the storage elastic modulus E'in the dynamic viscoelastic measurement at 10 ° C. is 2.0 MPa or more and 21 MPa or less, and the resin layer.
the pressure-sensitive adhesive layer has a breaking elongation of 30% or more in the shear adhesive force measurement at 23 ° C. and is stored in the dynamic viscoelastic measurement at 10 ° C.
An adhesive tape having an elastic modulus G'of 0.13 MPa or more and 7.0 MPa or less. The present invention will be described in detail below.
an adhesive tape having a base material and an adhesive layer laminated on at least one surface of the base material the present inventors were laminated on the base material layer and at least one surface of the base material layer. It has been found that by using a multilayer base material having a resin layer, the resin layer plays a role of dispersing stress when an impact is applied, and the repeated impact resistance of the adhesive tape can be improved. The present inventors further analyzed the factors that affect the impact resistance repeatedly in such an adhesive tape. As a result, the present inventors have stored elastic modulus E'in the dynamic viscoelasticity measurement at 10 ° C. of the base material layer, Young's modulus at 23 ° C. of the resin layer, and shear adhesive force at 23 ° C. of the pressure-sensitive adhesive layer.
the pressure-sensitive adhesive tape of the present invention has a multilayer base material and a pressure-sensitive adhesive layer laminated on at least one surface of the multilayer base material.
the multilayer base material has a base material layer and a resin layer laminated on at least one surface of the base material layer.
the resin layer plays a role of dispersing stress when subjected to an impact, and the adhesive tape of the present invention can have excellent repeated impact resistance.
the resin layer may be laminated on only one surface of the base material layer or may be laminated on both sides, but it is preferable that the resin layer is laminated on only one surface of the base material layer. ..
the lower limit of the storage elastic modulus E'in the dynamic viscoelasticity measurement at 10 ° C. is 2.0 MPa, and the upper limit is 21 MPa.
the base material layer can have an appropriate hardness, and the adhesive tape of the present invention has excellent repeated impact resistance. be able to.
the storage elastic modulus E'at 10 ° C. is 21 MPa or less, the flexibility of the base material layer is improved, and the base material layer is too hard to disperse stress when subjected to an impact.
the adhesive tape of the present invention can have excellent repetitive impact resistance.
the storage elastic modulus E'in the dynamic viscoelasticity measurement at 10 ° C. of the base material layer is determined by using a viscoelasticity spectrometer (for example, manufactured by IT Measurement Control Co., Ltd., DVA-200, etc.) at a constant rate of temperature rise and tension. It can be obtained as a storage elastic modulus E'at 10 ° C. when a dynamic viscoelastic spectrum at ⁇ 40 to 140 ° C. is measured under the conditions of mode of 5 ° C./min, strain of 0.1%, and frequency of 10 Hz.
a viscoelasticity spectrometer for example, manufactured by IT Measurement Control Co., Ltd., DVA-200, etc.
the method for adjusting the storage elastic modulus E'at 10 ° C. to the above range is not particularly limited.
a method for adjusting the gel fraction of the base material layer, the base material layer is a foam base material layer.
a method of adjusting the type or amount of foamed particles a method of using a copolymer having a structure derived from a vinyl aromatic monomer and a structure derived from a (meth) acrylic monomer as described later in the base material layer. And so on.
the base material layer is not particularly limited as long as the storage elasticity E'at 10 ° C. satisfies the above range, but preferably contains a copolymer having a structure derived from a (meth) acrylic monomer. , It is more preferable to contain a copolymer having a structure derived from a vinyl aromatic monomer and a structure derived from a (meth) acrylic monomer. When the base material layer contains these copolymers, it becomes easy to adjust the storage elastic modulus E'at 10 ° C. to the above range, and the repeated impact resistance of the adhesive tape is further improved.
vinyl aromatic monomer examples include styrene, ⁇ -methylstyrene, m-methylstyrene, p-methylstyrene, divinylbenzene, 1,1-diphenylethylene, 1-ethyl2-vinylbenzene, and 1-ethyl3-vinyl. Examples thereof include benzene, vinylnaphthalene and chlorostyrene. These vinyl aromatic monomers may be used alone or in combination of two or more. Of these, styrene is preferable because the repeated impact resistance of the adhesive tape is further improved.
the structure derived from the vinyl aromatic monomer refers to the structure represented by the following general formulas (1) and (2).
R 1 represents a substituent having an aromatic ring.
substituent R1 having an aromatic ring include a phenyl group, a methylphenyl group, a chlorophenyl group and the like.
the content of the structure derived from the vinyl aromatic monomer in the copolymer having the structure derived from the vinyl aromatic monomer and the structure derived from the (meth) acrylic monomer is not particularly limited, but is 1% by weight or more. It is preferably 30% by weight or less.
the content of the structure derived from the vinyl aromatic monomer is in the above range, the repeated impact resistance of the adhesive tape is further improved.
a more preferable lower limit of the content of the structure derived from the vinyl aromatic monomer is 1.5% by weight, a further preferable lower limit is 2% by weight, a further preferable lower limit is 3% by weight, and a particularly preferable lower limit is 3.5% by weight.
a more preferable upper limit is 15% by weight, and a further preferable upper limit is 8% by weight.
the copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer further has a structure derived from the monomer having a crosslinkable functional group.
a copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer has a crosslinkable functional group, the rubber elasticity of the copolymer is enhanced by cross-linking. It becomes easy to adjust the storage elastic coefficient E'at ° C to the above range, and the repeated impact resistance of the adhesive tape is further improved.
the crosslinkable functional group may or may not be crosslinked, but is more preferably crosslinked.
the structure derived from the monomer having a crosslinkable functional group refers to the structure represented by the following general formulas (3) and (4).
R 2 represents a substituent containing at least one functional group.
the functional group include a carboxyl group, a hydroxyl group, an epoxy group, a double bond, a triple bond, an amino group, an amide group, a nitrile group and the like.
the substituent R2 containing at least one functional group may contain an alkyl group, an ether group, a carbonyl group, an ester group, a carbonate group, an amide group, a urethane group and the like as its constituent elements.
the monomer having a crosslinkable functional group is not particularly limited, and for example, a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an epoxy group-containing monomer, a double bond-containing monomer, a triple bond-containing monomer, an amino group-containing monomer, and an amide group-containing monomer. , A nitrile group-containing monomer and the like.
These crosslinkable functional groups may be used alone or in combination of two or more.
the group consists of a carboxyl group-containing monomer, a hydroxyl group-containing monomer, an epoxy group-containing monomer, a double bond-containing monomer, a triple bond-containing monomer, and an amide group-containing monomer. At least one selected is preferred.
the carboxyl group-containing monomer include (meth) acrylic acid-based monomers such as (meth) acrylic acid.
the hydroxyl group-containing monomer include 4-hydroxybutyl (meth) acrylate and 2-hydroxyethyl (meth) acrylate.
the epoxy group-containing monomer include glycidyl (meth) acrylate and the like.
Examples of the double bond-containing monomer include allyl (meth) acrylate and hexanediol di (meth) acrylate.
Examples of the triple bond-containing monomer include propargyl (meth) acrylate and the like.
Examples of the amide group-containing monomer include (meth) acrylamide and the like. Of these, a carboxyl group-containing monomer and a hydroxyl group-containing monomer are preferable because the repeated impact resistance of the adhesive tape is further improved.
a (meth) acrylic acid-based monomer containing a carboxyl group and a (meth) acrylic acid-based monomer containing a hydroxyl group are more preferable, and (meth) acrylic acid, 4-hydroxybutyl (meth) acrylate, and 2-hydroxyethyl (meth) are preferable. Acrylic is more preferred.
the content of the structure derived from the crosslinkable functional group in the copolymer having the structure derived from the vinyl aromatic monomer and the structure derived from the (meth) acrylic monomer is not particularly limited, but is 0. It is preferably 1% by weight or more and 30% by weight or less.
the content of the structure derived from the monomer having a crosslinkable functional group is in the above range, the repeated impact resistance of the adhesive tape is further improved.
a more preferable lower limit of the content of the structure derived from the monomer having a crosslinkable functional group is 0.5% by weight, a further preferable lower limit is 1% by weight, a more preferable upper limit is 25% by weight, and a further preferable upper limit is 20% by weight. be.
the (meth) acrylic monomer may be a single monomer or may use a plurality of monomers.
the structure derived from the (meth) acrylic monomer refers to the structure represented by the following general formulas (5) and (6).
R 3 represents a side chain.
the side chain R 3 includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a dodecyl group and a lauryl group. Examples thereof include an isostearyl group.
Examples of the (meth) acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, and heptyl (meth). Meta) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, isostearyl (meth) acrylate And so on.
(meth) acrylic monomers may be used alone or in combination of two or more.
methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate are preferable because the repeated impact resistance of the adhesive tape is further improved.
Ethyl acrylates, butyl acrylates and 2-ethylhexyl acrylates are even more preferred.
the (meth) acrylic monomer it is preferable to use a (meth) acrylic monomer having 2 or less side chain carbon atoms.
the (meth) acrylic monomer having 2 or less side chain carbon atoms When the (meth) acrylic monomer having 2 or less side chain carbon atoms is used, the entanglement between the obtained copolymer chains is increased, the cohesive force is improved, and the storage elastic modulus E'at the above 10 ° C. is increased. It becomes easy to adjust to the above range, and the repeated impact resistance of the adhesive tape is further improved and the heat resistance is also improved.
Examples of the (meth) acrylic monomer having 2 or less side chain carbon atoms include methyl (meth) acrylate and ethyl (meth) acrylate, and methyl acrylate and ethyl acrylate are particularly preferable.
the content of the structure derived from the (meth) acrylic monomer in the copolymer having the structure derived from the vinyl aromatic monomer and the structure derived from the (meth) acrylic monomer is not particularly limited, and the content of the structure derived from the (meth) acrylic monomer is not particularly limited. The effect may be exhibited, but it is preferably 30% by weight or more and 99% by weight or less.
the content of the structure derived from the (meth) acrylic monomer is more preferably 40% by weight or more and 98% by weight or less, and further preferably 50% by weight or more and 97% by weight or less.
the content of the (meth) acrylic monomer having 2 or less side chain carbon atoms is particularly limited.
the preferred lower limit is 5% by weight and the preferred upper limit is 90% by weight.
the content of the (meth) acrylic monomer having 2 or less side chain carbon atoms is 5% by weight or more, the effect of improving the cohesive force is likely to be exhibited. If the content of the (meth) acrylic monomer having 2 or less side chain carbon atoms is 90% by weight or less, the cohesive force becomes too high, the flexibility becomes low, and the flexibility as an adhesive tape is lost. Can be prevented.
a more preferable lower limit of the content of the (meth) acrylic monomer having 2 or less side chain carbon atoms is 10% by weight, a further preferable lower limit is 20% by weight, a further preferable lower limit is 25% by weight, and a particularly preferable lower limit is 30% by weight.
the more preferable upper limit is 85% by weight, the further preferable upper limit is 80% by weight, the still more preferable upper limit is 75% by weight, and the particularly preferable upper limit is 70% by weight.
the copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer is not particularly limited as long as it has each structure as described above, and is a random copolymer. It may be a block copolymer or a block copolymer. From the viewpoint of further enhancing the flexibility of the base material layer, a random copolymer is preferable, and from the viewpoint of further enhancing the balance between the hardness and flexibility of the base material layer, a block copolymer is preferable.
the block copolymer is a copolymer containing a rigid structure (hereinafter, also referred to as "hard block”) and a flexible structure (hereinafter, also referred to as "soft block”).
the block copolymer may have a non-uniform phase-separated structure in which two blocks are difficult to be compatible with each other and islands formed by agglomeration of the hard blocks are scattered in the sea of the soft blocks. Since the islands serve as pseudo-crosslinking points, rubber elasticity can be imparted to the block copolymer, so that the repeated impact resistance of the adhesive tape is further improved.
the crosslinkable functional group as described above into the hard block, the repeated impact resistance of the adhesive tape is further improved.
the adhesive tape has excellent repeat impact resistance. be able to. It is considered that this is because the same interaction as the above-mentioned phase-separated structure works at a very small scale such as the nano level and the molecular level.
the block copolymer contains a structure derived from the vinyl aromatic monomer in the hard block and a structure derived from the (meth) acrylic monomer in the soft block.
the hard block is not particularly limited as long as it has a rigid structure, and in addition to the structure derived from the vinyl aromatic monomer, for example, a compound having a cyclic structure, a compound having a short side chain substituent, or the like can be used. It may have a derived structure.
the soft block may have a structure derived from a monomer other than the (meth) acrylic monomer as long as the effect of the present invention is not lost.
the block copolymer may have any structure such as a diblock structure or a triblock structure, but since the repeated impact resistance of the adhesive tape is further improved, the soft block between the hard blocks is further improved. It is preferable to have a triblock structure having.
the block copolymer may be a graft copolymer in which the hard block and the soft block are separated into a main chain and a side chain. Examples of the graft copolymer include a styrene macromer- (meth) acrylic monomer copolymer and the like.
the content of the hard block in the block copolymer is not particularly limited, but is preferably 1% by weight or more and 40% by weight or less.
the content of the hard block is in the above range, the repeated impact resistance of the adhesive tape is further improved and the heat resistance is also improved.
the more preferable lower limit of the content of the hard block is 2% by weight, the more preferable lower limit is 2.5% by weight, and the particularly preferable lower limit is 3% by weight.
a more preferable upper limit of the content of the hard block is 35% by weight, a further preferable upper limit is 30% by weight, a further preferable upper limit is 26% by weight, a further preferable upper limit is 20% by weight, and a particularly preferable upper limit is 17% by weight, particularly preferable.
the upper limit is 8% by weight.
the weight average molecular weight (Mw) of the copolymer having a structure derived from the vinyl aromatic monomer and a structure derived from the (meth) acrylic monomer is not particularly limited, but is preferably 50,000 or more and 800,000 or less. ..
the more preferable lower limit of the weight average molecular weight is 75,000, and the more preferable upper limit is 600,000.
the weight average molecular weight can be determined, for example, by a GPC (Gel Permeation Chromatography) method in terms of standard polystyrene.
the raw material monomers of the hard block and the soft block are used in the presence of a polymerization initiator.
the hard block and the soft block may be obtained by radical reaction, respectively, and then the two may be reacted or copolymerized. Further, after obtaining the hard block, the raw material monomer of the soft block may be continuously added and copolymerized.
a solution mixed with the raw material monomers may be subjected to a radical reaction in the presence of a polymerization initiator.
the method for causing the radical reaction that is, the polymerization method
a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
the base material layer contains additives such as antistatic agents, mold release agents, antioxidants, weathering agents, and crystal nucleating agents, and resin modifiers such as polyolefins, polyesters, polyamides, and elastomers. good.
the base material layer has at least one peak in each of a region of 10 ° C. or lower and a region of 50 ° C. or higher when DSC measurement (differential scanning calorimetry) is performed in the atmosphere at a temperature rise rate of 10 ° C./min. It is preferable to have.
the base material layer has at least one peak in a region of 10 ° C. or lower and a region of 50 ° C. or higher when DSC measurement is performed, the base material layer is a block having two blocks as described above. It can be said that it contains a polymer. From the viewpoint of further enhancing the balance between the hardness and flexibility of the base material layer, it is preferable that the base material layer contains the block copolymer in this way.
the peak in the region of 10 ° C. or lower when the DSC measurement is performed may be referred to as the peak derived from the soft block, and the peak in the region of 50 ° C. or higher may be referred to as the peak derived from the hard block.
the peak region can be adjusted by the type of the raw material monomer of the hard block and the soft block.
a differential scanning calorimeter for example, manufactured by TA Instruments, DSC 2920, etc.
a temperature rise rate of 10 ° C./min a temperature rise rate of 10 ° C./min
the number of cycles is 1. It can be done under the condition of times.
the base material layer may have a single-layer structure or a multi-layer structure.
the base material layer is preferably a foam base material layer. Since the base material layer is the foam base material layer, the flexibility is improved, and it is possible to prevent the base material layer from being too hard to disperse stress when subjected to an impact. This further improves the repeated impact resistance of the adhesive tape.
the foam base material layer may have an open cell structure or a closed cell structure, but is preferably a closed cell structure.
the expansion ratio of the foam base material layer is not particularly limited, but the preferable lower limit is 1.1 times and the preferable upper limit is 10 times.
the foaming ratio is in the above range, the balance between the hardness and the flexibility of the foam base material layer can be further improved, so that the repeated impact resistance of the adhesive tape is further improved.
the more preferable lower limit of the foaming ratio is 1.3 times, the more preferable upper limit is 7 times, the further preferable lower limit is 1.5 times, and the further preferable upper limit is 5 times.
the foaming magnification of the foam base material layer is the reciprocal of the density of the foam base material layer, and is measured using an electronic hydrometer (for example, ED120T manufactured by Mirage Co., Ltd.) in accordance with JIS K 7222. can.
an electronic hydrometer for example, ED120T manufactured by Mirage Co., Ltd.
the average bubble diameter of the foam base material layer is not particularly limited, but is preferably 80 ⁇ m or less. When the average bubble diameter is 80 ⁇ m or less, the balance between the hardness and the flexibility of the foam base material layer can be further improved, so that the repeated impact resistance of the adhesive tape is further improved.
the average bubble diameter is more preferably 60 ⁇ m or less, and further preferably 55 ⁇ m or less.
the lower limit of the average cell diameter is not particularly limited, but is preferably 20 ⁇ m or more, and more preferably 30 ⁇ m or more, from the viewpoint of ensuring the flexibility of the foam base material layer.
the average bubble diameter of the foam base material layer can be measured by the following method.
the foam base material layer is cut into 50 mm squares, immersed in liquid nitrogen for 1 minute, and then cut in a plane perpendicular to the thickness direction of the foam base material layer using a razor blade. Then, using a digital microscope (for example, "VHX-900" manufactured by KEYENCE Corporation), a magnified photograph of the cut surface was taken at a magnification of 200 times, and the most bubbles existing in the range of thickness ⁇ 2 mm were taken. Measure a long bubble diameter (bubble diameter). This operation is repeated 5 times, and the average bubble diameter is calculated by averaging all the obtained bubble diameters.
VHX-900 manufactured by KEYENCE Corporation
the base material layer preferably has a gel fraction of 90% by weight or less.
the gel fraction of the base material layer is within the above range, the repeated impact resistance of the adhesive tape is further improved.
the more preferable upper limit of the gel fraction is 85% by weight, and the more preferable upper limit is 80% by weight.
the lower limit of the gel fraction is not particularly limited, but is, for example, 10% by weight or more, particularly 20% by weight or more, and particularly 35% by weight or more.
the gel fraction can be adjusted by cross-linking the resin constituting the base material layer.
the gel fraction of the base material layer can be measured by the following method.
the base material layer has a cross-linked structure formed between the main chains of the resin constituting the base material layer by adding a cross-linking agent.
a cross-linking agent By forming a crosslinked structure between the main chains of the resin constituting the base material layer, the stress applied intermittently can be dispersed, and the repeated impact resistance of the adhesive tape is further improved and the heat resistance is also improved. ..
the cross-linking agent is not particularly limited, and can be appropriately selected depending on the functional group of the resin constituting the base material layer. Specific examples thereof include isocyanate-based cross-linking agents, aziridine-based cross-linking agents, epoxy-based cross-linking agents, and metal chelate-type cross-linking agents. Among them, an epoxy-based cross-linking agent or an isocyanate-based cross-linking agent is preferable because a resin having an alcoholic hydroxyl group or a carboxyl group that can further improve flexibility can be cross-linked.
the isocyanate-based cross-linking agent When the isocyanate-based cross-linking agent is used, the alcoholic hydroxyl group or carboxyl group in the resin constituting the base material layer is crosslinked with the isocyanate group of the isocyanate-based cross-linking agent.
the epoxy-based cross-linking agent When the epoxy-based cross-linking agent is used, the carboxyl group in the resin constituting the base material layer and the epoxy group of the epoxy-based cross-linking agent are cross-linked.
the amount of the cross-linking agent added is not particularly limited, but is preferably 0.01 parts by weight or more and 10 parts by weight or less, preferably 0.1 parts by weight or more and 7 parts by weight with respect to 100 parts by weight of the resin constituting the base material layer. The following are more preferable.
the thickness of the base material layer is not particularly limited, but a preferable lower limit is 40 ⁇ m and a preferable upper limit is 2900 ⁇ m.
a preferable lower limit is 40 ⁇ m and a preferable upper limit is 2900 ⁇ m.
the adhesive tape can be used for portable electronic device parts and automobiles. It can be suitably used for fixing electronic device parts such as electronic device parts.
the more preferable lower limit of the thickness of the base material layer is 60 ⁇ m
the more preferable upper limit is 1900 ⁇ m
the further preferable lower limit is 80 ⁇ m
the further preferable upper limit is 1400 ⁇ m
the particularly preferable lower limit is.
100 ⁇ m a particularly preferred upper limit is 1000 ⁇ m.
the method for producing the base material layer is not particularly limited.
examples of the method for producing the foam base material layer include a method of producing by the action of foaming gas and a method of producing by blending hollow spheres in a raw material matrix.
the foam base material layer produced by the latter method is called syntactic foam, and is excellent in strength, flexibility and heat resistance. Therefore, the foam base material layer may be syntactic foam. preferable.
the foam base material layer is syntactic foam, it becomes a closed cell type foam having a uniform size distribution, so that the density of the entire foam base material layer becomes more constant, and the strength, flexibility and Heat resistance is further improved.
syntactic foam exhibits higher heat resistance than other foams because it is less likely to cause irreversible disintegration under high temperature and high pressure.
Syntactic foam includes those having a foamed structure made of hollow inorganic particles and those having a foamed structure made of hollow organic particles. From the viewpoint of flexibility, syntactic foam having a foamed structure made of hollow organic particles. Foam is preferred.
Examples of the hollow organic particles include Expancel DU series (manufactured by Nippon Philite Co., Ltd.), Advancel EM series (manufactured by Sekisui Chemical Co., Ltd.) and the like. Among them, since it is easy to design the bubble diameter after foaming in a region with higher effect, Expandel 461-DU-20 (average bubble diameter after foaming under optimum conditions 20 ⁇ m), Expandel 461-DU- 40 (average cell diameter after foaming under optimum conditions 40 ⁇ m), Expandel 043-80 (average cell diameter after foaming under optimum conditions 80 ⁇ m), Advansel EML101 (average cell diameter after foaming under optimum conditions 50 ⁇ m) ) Is preferable.
the content of the hollow organic particles is not particularly limited, but the preferable lower limit is 0.1 parts by weight, the preferable upper limit is 10 parts by weight, and the more preferable lower limit is 0 with respect to 100 parts by weight of the resin constituting the foam base material layer. .3 parts by weight, more preferably 7 parts by weight.
the expansion ratio of the foam base material layer can be adjusted in an appropriate range.
the foaming agent is not particularly limited, and a conventionally known foaming agent such as a pyrolytic foaming agent can be used.
the resin layer has a lower limit of Young's modulus at 23 ° C. of 500 MPa.
the preferred lower limit of Young's modulus at 23 ° C. is 1000 MPa, and the more preferable lower limit is 2000 MPa.
the upper limit of the Young's modulus at 23 ° C. is not particularly limited, but from the viewpoint of ensuring flexibility, a preferable upper limit is 4000 MPa, and a more preferable upper limit is 3000 MPa.
a desktop precision universal testing machine for example, Shimadzu Corporation, Autograph AGS-X series, etc.
JIS-K-7161 JIS-K-7161.
a test piece cut into a width of 10 mm and a length of 100 mm is chucked at an interval of 50 mm, and a stress-strain curve when pulled at a speed of 200 mm / min is measured, and the strain is from 1% to 5%. Young's modulus can be obtained by calculating the average slope.
the method of adjusting the Young's modulus at 23 ° C. to the above range is not particularly limited, and examples thereof include a method of selecting a resin constituting the resin layer. More specifically, it is preferable to select a resin having a rigid component such as an aromatic ring in the main chain.
the resin constituting the resin layer preferably has heat resistance.
the resin constituting the heat-resistant resin layer include polyester resins such as polyethylene terephthalate, acrylic resins, silicone resins, phenol resins, polyimides, polycarbonates, and polyolefin resins. Among them, polyester-based resin, polyimide, and polyolefin resin are preferable, polyester-based resin is more preferable, and polyethylene terephthalate is further preferable, because the repeated impact resistance of the adhesive tape is further improved.
the resin layer may be colored.
coloring the resin layer it is possible to impart light-shielding properties to the adhesive tape.
the method of coloring the resin layer is not particularly limited, and for example, a method of kneading particles such as carbon black or titanium oxide or fine bubbles into the resin constituting the resin layer, or applying ink to the surface of the resin layer. The method and the like can be mentioned.
the resin layer may contain conventionally known particles and additives such as inorganic particles, conductive particles, plasticizers, tackifiers, ultraviolet absorbers, antioxidants, foaming agents, organic fillers, and inorganic fillers, if necessary. May be contained.
the thickness of the resin layer is not particularly limited, but the preferred lower limit is 5 ⁇ m and the preferred upper limit is 100 ⁇ m.
the thickness of the resin layer is not particularly limited, but the preferred lower limit is 5 ⁇ m and the preferred upper limit is 100 ⁇ m.
the more preferable lower limit of the thickness of the resin layer is 10 ⁇ m, and the more preferable upper limit is 70 ⁇ m.
the pressure-sensitive adhesive layer may be laminated on only one surface of the multilayer base material, or may be laminated on both sides.
the pressure-sensitive adhesive layers on both sides may have the same composition and physical properties, or may have different compositions and physical properties.
the pressure-sensitive adhesive layer has a lower limit of breaking elongation of 30% in the shear adhesive force measurement at 23 ° C.
the preferable lower limit of the elongation at break at 23 ° C. is 35%.
the upper limit of the elongation at break at 23 ° C. is not particularly limited, but from the viewpoint of ensuring strength, the preferable upper limit is 80%, and the more preferable upper limit is 70%.
test piece is based on JIS-Z-0237, and is a tabletop precision universal testing machine (for example, Autograph AGS-X manufactured by Shimadzu Corporation). It can be calculated as follows using the series etc.).
two polycarbonate plates of 55 mm ⁇ 65 mm ⁇ thickness of 1 mm are attached to both sides of the test piece and pressed at 10 kg for 10 seconds to bond the two polycarbonate plates. Then, the mixture is allowed to stand at 23 ° C. for 3 hours to obtain a test sample.
test sample was pulled in the length direction of the test piece at a speed of 500 mm / min under the above-mentioned device in an environment of 23 ° C., and the tensile elongation when the test piece broke was recorded, and the elongation rate with respect to the length of the test piece was recorded.
the breaking elongation in the shear adhesive force measurement of the adhesive layer at 23 ° C. is calculated.
the elongation at break in the shear adhesive force measurement is dominated by the influence of the most stretchable layer when the laminated body is the measurement target. Even if a layer having a small elongation due to a shearing force is included in the laminate to be measured, the presence of a layer having a small elongation due to a shearing force does not significantly affect the overall value. Therefore, when it is difficult to adjust the above-mentioned test piece, the breaking elongation of the most stretchable layer can be estimated by performing the same measurement on the laminated body itself.
the preferable lower limit of the gel fraction is 10% by weight, and the preferable upper limit is 90% by weight.
the gel fraction is 10% by weight or more, the adhesive layer is less likely to be deformed when subjected to an impact, and the repeated impact resistance of the adhesive tape is further improved.
the gel fraction is 90% by weight or less, the flexibility of the pressure-sensitive adhesive layer is improved, and it is possible to prevent the pressure-sensitive adhesive layer from being too hard to disperse stress when subjected to an impact. .. This further improves the repeated impact resistance of the adhesive tape.
the more preferable lower limit of the gel fraction is 20% by weight, and the more preferable upper limit is 80% by weight.
the gel fraction of the pressure-sensitive adhesive layer can be measured by the same method as the gel fraction of the base material layer.
the lower limit of the storage elastic modulus G'in the dynamic viscoelasticity measurement at 10 ° C. is 0.13 MPa
the upper limit is 7.0 MPa.
the storage elastic modulus G'at 10 ° C. is 0.13 MPa or more
the adhesive layer is less likely to be deformed when subjected to an impact, and the repeated impact resistance of the adhesive tape is further improved.
the storage elastic modulus G'at 10 ° C. is 7.0 MPa or less
the flexibility of the pressure-sensitive adhesive layer is improved, and the pressure-sensitive adhesive layer is too hard to disperse stress when subjected to an impact. You can prevent that. This further improves the repeated impact resistance of the adhesive tape.
the preferable lower limit of the storage elastic modulus G'at 10 ° C. of the pressure-sensitive adhesive layer is 0.25 MPa, the preferable upper limit is 5.0 MPa, the more preferable lower limit is 0.3 MPa, and the more preferable upper limit is 4.0 MPa.
the storage elastic modulus G'at 10 ° C. of the pressure-sensitive adhesive layer can be measured by the same method as the storage elastic modulus of the base material layer except that it is measured in the constant-speed temperature-increasing shear mode.
the method for adjusting the breaking elongation at 23 ° C., the gel fraction, and the storage elastic modulus G'at 10 ° C. within the above ranges is not particularly limited, and for example, the resin constituting the pressure-sensitive adhesive layer and the addition thereof. Examples include a method of selecting an agent. More specifically, as the pressure-sensitive adhesive layer, it is preferable to use an acrylic pressure-sensitive adhesive layer containing an acrylic copolymer, a pressure-imparting resin, and a cross-linking agent as described later.
the pressure-sensitive adhesive layer is not particularly limited, and examples thereof include an acrylic pressure-sensitive adhesive layer, a rubber-based pressure-sensitive adhesive layer, a urethane pressure-sensitive adhesive layer, and a silicone-based pressure-sensitive adhesive layer.
an acrylic pressure-sensitive adhesive layer containing an acrylic copolymer is preferable because it has excellent heat resistance and can be adhered to a wide variety of adherends.
the acrylic copolymer can be obtained by copolymerizing a monomer mixture containing butyl acrylate and / or 2-ethylhexyl acrylate from the viewpoint of improving the initial tack and making it easy to attach at low temperature. preferable. Above all, it is more preferable to obtain it by copolymerizing a monomer mixture containing butyl acrylate and 2-ethylhexyl acrylate.
the preferable lower limit of the content of the butyl acrylate in the total monomer mixture is 40% by weight, and the preferable upper limit is 80% by weight.
the preferable lower limit of the content of the 2-ethylhexyl acrylate in the total monomer mixture is 10% by weight, and the preferable upper limit is 100% by weight.
the monomer mixture may contain other copolymerizable monomers other than butyl acrylate and 2-ethylhexyl acrylate, if necessary.
the other copolymerizable monomer include (meth) acrylic acid alkyl esters having 1 to 18 carbon atoms in the alkyl group, functional monomers and the like.
the (meth) acrylic acid alkyl ester having 1 to 18 carbon atoms in the alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and (meth) acrylic acid.
Examples thereof include isopropyl, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, tridecyl methacrylate, and stearyl (meth) acrylate.
Examples of the functional monomer include hydroxyalkyl (meth) acrylate, alkoxyalkyl (meth) acrylate, glycerin dimethacrylate, glycidyl (meth) acrylate, 2-methacryloyloxyethyl isocyanate, (meth) acrylic acid, and itaconic acid. , Maleic anhydride, crotonic acid, maleic acid, fumaric acid and the like.
the monomer mixture may be subjected to a radical reaction in the presence of a polymerization initiator.
a method of radically reacting the monomer mixture that is, a polymerization method
a conventionally known method is used, and examples thereof include solution polymerization (boiling point polymerization or constant temperature polymerization), emulsion polymerization, suspension polymerization, bulk polymerization and the like.
the weight average molecular weight (Mw) of the acrylic copolymer is not particularly limited, but the preferable lower limit is 400,000 and the preferable upper limit is 1.5 million. By setting the weight average molecular weight of the acrylic copolymer in the above range, high adhesive strength can be exhibited. From the viewpoint of further improving the adhesive strength, the more preferable lower limit of the weight average molecular weight is 500,000, and the more preferable upper limit is 1.4 million.
the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) of the acrylic copolymer is preferably 10.0.
Mw / Mn is 10.0 or less, the ratio of the small molecule component is suppressed, the pressure-sensitive adhesive layer is softened at a high temperature, the bulk strength is lowered, and the adhesive strength is suppressed.
the more preferable upper limit of Mw / Mn is 5.0, and the more preferable upper limit is 3.0.
the pressure-sensitive adhesive layer may contain a pressure-sensitive adhesive resin.
the tackifier resin include rosin ester resin, hydrogenated rosin resin, terpene resin, terpene phenol resin, Kumaron inden resin, alicyclic saturated hydrocarbon resin, C5 petroleum resin, and C9 resin. Examples thereof include petroleum resins and C5-C9 copolymerized petroleum resins. These tackifier resins may be used alone or in combination of two or more.
the content of the tackifier resin is not particularly limited, but the preferable lower limit is 10 parts by weight and the preferable upper limit is 60 parts by weight with respect to 100 parts by weight of the resin (for example, acrylic copolymer) which is the main component of the pressure-sensitive adhesive layer. ..
the resin for example, acrylic copolymer
the content of the pressure-sensitive adhesive resin is 10 parts by weight or more, the pressure-sensitive adhesive layer can exhibit high adhesive strength.
the content of the pressure-sensitive adhesive resin is 60 parts by weight or less, it is possible to suppress a decrease in adhesive strength or tackiness due to the hardening of the pressure-sensitive adhesive layer.
the pressure-sensitive adhesive layer has a cross-linked structure formed between the main chains of the resin (for example, the acrylic copolymer, the pressure-sensitive adhesive resin, etc.) constituting the pressure-sensitive adhesive layer by adding a cross-linking agent.
a cross-linking agent for example, the acrylic copolymer, the pressure-sensitive adhesive resin, etc.
the above-mentioned cross-linking agent is not particularly limited, and examples thereof include an isocyanate-based cross-linking agent, an aziridine-based cross-linking agent, an epoxy-based cross-linking agent, and a metal chelate-type cross-linking agent. Of these, isocyanate-based cross-linking agents are preferable.
the isocyanate group of the isocyanate-based cross-linking agent and the alcohol in the resin constituting the pressure-sensitive adhesive layer (for example, the acrylic copolymer, the pressure-sensitive adhesive resin, etc.)
the pressure-sensitive adhesive layer is crosslinked by reacting with the sex hydroxylate.
the amount of the cross-linking agent added is preferably 0.01 to 10 parts by weight, preferably 0.1 to 7 parts by weight, based on 100 parts by weight of the resin (for example, the acrylic copolymer) which is the main component of the pressure-sensitive adhesive layer. Is more preferable.
the pressure-sensitive adhesive layer may contain a silane coupling agent for the purpose of improving the pressure-sensitive adhesive force.
the silane coupling agent is not particularly limited, and examples thereof include epoxysilanes, acrylicsilanes, methacrylsilanes, aminosilanes, and isocyanatesilanes.
the pressure-sensitive adhesive layer may contain a coloring material for the purpose of imparting light-shielding properties.
the coloring material is not particularly limited, and examples thereof include carbon black, aniline black, and titanium oxide. Of these, carbon black is preferable because it is relatively inexpensive and chemically stable.
the pressure-sensitive adhesive layer may contain conventionally known particles and additives such as inorganic particles, conductive particles, antioxidants, foaming agents, organic fillers, and inorganic fillers, if necessary.
the thickness of the pressure-sensitive adhesive layer is not particularly limited, but a preferable lower limit is 0.01 mm, a preferable upper limit is 0.1 mm, a more preferable lower limit is 0.015 mm, and a more preferable upper limit is 0.09 mm.
a preferable lower limit is 0.01 mm
a preferable upper limit is 0.1 mm
a more preferable lower limit is 0.015 mm
a more preferable upper limit is 0.09 mm.
the adhesive tape of the present invention preferably has a lower limit of breaking elongation of 30% in the shear adhesive force measurement at 23 ° C.
the breaking elongation of the adhesive tape of the present invention in the shear adhesive force measurement at 23 ° C. can be adjusted, for example, by changing the breaking elongation in the shear adhesive force measurement of the pressure-sensitive adhesive layer at 23 ° C.
the thickness of the entire adhesive tape of the present invention is not particularly limited, but a preferable lower limit is 0.04 mm, a more preferable lower limit is 0.05 mm, a preferable upper limit is 2 mm, and a more preferable upper limit is 1.5 mm.
a preferable lower limit is 0.04 mm
a more preferable lower limit is 0.05 mm
a preferable upper limit is 2 mm
a more preferable upper limit is 1.5 mm.
the method for producing the adhesive tape of the present invention is not particularly limited, and examples thereof include the following methods. First, a pressure-sensitive adhesive solution is applied to a release film and dried to form a pressure-sensitive adhesive layer. Next, an unfoamed base material layer is manufactured, and a resin layer is laminated on the unfoamed base material layer to form a laminate. Then, an adhesive layer is attached to both sides of the obtained laminate, and the unfoamed base material is foamed by heating to form a foam base material layer, and an adhesive tape is manufactured.
the use of the adhesive tape of the present invention is not particularly limited, but it is preferably used for assembling or fixing electronic device parts such as portable electronic device parts and in-vehicle electronic device parts because it is excellent in repeated impact resistance.
Example 1 Production of unfoamed substrate layer 0.902 g of 1,6-hexanedithiol, 1.83 g of carbon disulfide, and 11 mL of dimethylformamide were placed in a two-necked flask and stirred at 25 ° C. To this, 2.49 g of triethylamine was added dropwise over 15 minutes, and the mixture was stirred at 25 ° C. for 3 hours. Then, 2.75 g of methyl- ⁇ -bromophenylacetic acid was added dropwise over 15 minutes, and the mixture was stirred at 25 ° C. for 4 hours.
the blending amount of the mixture was adjusted so that the content of the hard block in the obtained block copolymer was 3% by weight and the content of the soft block was 97% by weight.
a part of the reaction solution is collected, 4000 parts by weight of n-hexane is added thereto, and the mixture is stirred to precipitate the reaction product, then the unreacted monomer and solvent are filtered, and the reaction product is dried under reduced pressure at 70 ° C.
the block copolymer was obtained.
the weight average molecular weight of the obtained block copolymer was measured by the GPC method and found to be 390,000.
the obtained block copolymer was dissolved in ethyl acetate so that the solid content was 35%.
ethyl acetate For 100 parts by weight of the block copolymer, 3.3 parts by weight of Expandel 461-DU-40 (461DU40) (manufactured by Nippon Philite) as a foaming agent (foaming particles) and Tetrad C (Mitsubishi Gas Chemical Company) as a cross-linking agent. (Manufactured by the same company) 0.15 parts by weight was added and further sufficiently stirred to obtain a foam substrate layer solution.
Expandel 461-DU-40 461DU40
Tetrad C Mitsubishi Gas Chemical Company
the obtained foam base material layer solution was applied onto a corona-treated surface of a resin film as the resin layer I (a polyethylene terephthalate (PET) film having a thickness of 23 ⁇ m with one side treated with corona, and a Young's modulus of 2026 MPa at 23 ° C.). After coating and drying at 90 ° C. for 7 minutes, a laminate of the unfoamed base material layer A and the resin layer I was obtained. The thickness of the unfoamed base material layer A was adjusted to 127 ⁇ m when the unfoamed base material layer A was allowed to stand in an environment of 40 ° C. for 48 hours and then heated at 130 ° C. for 1 minute.
a resin film as the resin layer I a polyethylene terephthalate (PET) film having a thickness of 23 ⁇ m with one side treated with corona, and a Young's modulus of 2026 MPa at 23 ° C.
the weight average molecular weight of the obtained acrylic copolymer was measured by the GPC method using "2690 Separations Model" manufactured by Waters as a column, and it was 910,000. With respect to 100 parts by weight of the solid content of the acrylic copolymer contained in the obtained solution of the acrylic copolymer, 15 parts by weight of the polymerized rosin ester resin having a softening point of 135 ° C. and the terpenephenol resin 10 having a softening point of 160 ° C. By weight, 10 parts by weight of a rosin ester resin having a softening point of 75 ° C. was added.
test sample was pulled in the length direction of the test piece at a speed of 500 mm / min under the above-mentioned device in an environment of 23 ° C., and the tensile elongation when the test piece broke was recorded, and the elongation rate with respect to the length of the test piece was recorded.
the elongation at break in the shear adhesive force measurement of the adhesive layer at 23 ° C. was calculated.
Examples 2 to 20, Comparative Examples 1 to 7 An adhesive tape was obtained in the same manner as in Example 1 except that the base material layer (foam base material layer), the pressure-sensitive adhesive layer, and the resin layer were changed as shown in Tables 4 to 5.
the details of the base material layer (foam base material layer) are shown in Table 1, the details of the pressure-sensitive adhesive layer are shown in Table 2, and the details of the resin layer are shown in Table 3.
the AS-6S (styrene macromonomer solution (50% toluene solution) manufactured by Toa Synthetic Co., Ltd.) of the base material layer (foam base material layer R) used in Comparative Example 7 shows the amount of styrene macromonomer solid in the table. It was adjusted and used so as to have the stated value.
the raw materials in the table are as follows.
the test sample is placed in a TD-1000A drum type rotary drop tester (manufactured by Shinei Denshi Keiki Co., Ltd.) and rotated at a speed of 12 rpm while maintaining a room temperature environment of 23 ° C. to rotate the test sample to 1 m. It was repeatedly dropped from the height of.
the case where the number of drops when the polycarbonate plate was peeled off was more than 1500 times was evaluated as ⁇
the case where the number of drops was more than 1000 times and 1500 times or less was evaluated as ⁇
the case where the number of drops was 1000 times or less was evaluated as x.

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Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Adhesive Tapes (AREA)
Laminated Bodies (AREA)
Adhesives Or Adhesive Processes (AREA)

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