JP2021169594A - Aqueous pressure-sensitive adhesive, pressure-sensitive adhesive sheet, and method for producing aqueous pressure-sensitive adhesive - Google Patents
Aqueous pressure-sensitive adhesive, pressure-sensitive adhesive sheet, and method for producing aqueous pressure-sensitive adhesive Download PDFInfo
- Publication number
- JP2021169594A JP2021169594A JP2020074182A JP2020074182A JP2021169594A JP 2021169594 A JP2021169594 A JP 2021169594A JP 2020074182 A JP2020074182 A JP 2020074182A JP 2020074182 A JP2020074182 A JP 2020074182A JP 2021169594 A JP2021169594 A JP 2021169594A
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- JP
- Japan
- Prior art keywords
- sensitive adhesive
- pressure
- emulsion
- acrylic copolymer
- acrylic
- Prior art date
- Legal status (The legal status 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 status listed.)
- Granted
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- 239000004820 Pressure-sensitive adhesive Substances 0.000 title claims abstract description 175
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 40
- 229920006243 acrylic copolymer Polymers 0.000 claims abstract description 128
- 239000000839 emulsion Substances 0.000 claims abstract description 125
- 229920005989 resin Polymers 0.000 claims abstract description 117
- 239000011347 resin Substances 0.000 claims abstract description 117
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 94
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 claims abstract description 33
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 claims abstract description 33
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000178 monomer Substances 0.000 claims description 87
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 80
- -1 polyethylene terephthalate Polymers 0.000 claims description 51
- 239000003995 emulsifying agent Substances 0.000 claims description 32
- 230000009477 glass transition Effects 0.000 claims description 31
- 239000010410 layer Substances 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 16
- 238000007720 emulsion polymerization reaction Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 6
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 6
- 239000004908 Emulsion polymer Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000000853 adhesive Substances 0.000 abstract description 91
- 230000001070 adhesive effect Effects 0.000 abstract description 91
- 239000000203 mixture Substances 0.000 description 59
- 239000002994 raw material Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 23
- 238000012360 testing method Methods 0.000 description 20
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 16
- 238000000034 method Methods 0.000 description 16
- 238000006116 polymerization reaction Methods 0.000 description 15
- 150000002148 esters Chemical class 0.000 description 14
- 239000000123 paper Substances 0.000 description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000005191 phase separation Methods 0.000 description 13
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- 239000004698 Polyethylene Substances 0.000 description 12
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- 239000006185 dispersion Substances 0.000 description 11
- 238000011156 evaluation Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000003505 polymerization initiator Substances 0.000 description 11
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 9
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- 239000000523 sample Substances 0.000 description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
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- 238000003786 synthesis reaction Methods 0.000 description 8
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 6
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
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- 239000002904 solvent Substances 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 239000005977 Ethylene Substances 0.000 description 5
- 239000004840 adhesive resin Substances 0.000 description 5
- 125000000129 anionic group Chemical group 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
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- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 4
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- 239000012790 adhesive layer Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 3
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Images
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Abstract
Description
本発明は、水性感圧式接着剤、感圧式接着シート、および水性感圧式接着剤の製造方法に関する。 The present invention relates to a water-based pressure-sensitive adhesive, a pressure-sensitive adhesive sheet, and a method for producing a water-based pressure-sensitive adhesive.
近年、安全衛生および環境に対する配慮から、感圧式接着剤において、溶剤型から水性型への移行が進んでいる。しかしながら、水性型感圧式接着剤は塗工後の乾燥工程において分散粒子同士が融着して乾燥被膜を形成するため、溶剤型感圧式接着剤に比べて、塗工および乾燥後に得られる膜(感圧式接着層)の緻密さに欠ける傾向がある。そのため、水性型感圧式接着剤を用いた感圧式接着シートは、溶剤型感圧式接着剤を用いた感圧式接着シートに比べて、被着体、特にポリオレフィン系樹脂等の被着体に対する曲面貼付性に劣る傾向がある。 In recent years, in consideration of safety and health and the environment, pressure-sensitive adhesives are shifting from solvent-based adhesives to water-based adhesives. However, since dispersed particles are fused to each other to form a dry film in the drying step after coating, the water-based pressure-sensitive adhesive is a film obtained after coating and drying (compared to the solvent-based pressure-sensitive adhesive). The pressure-sensitive adhesive layer) tends to lack precision. Therefore, the pressure-sensitive adhesive sheet using the water-based pressure-sensitive adhesive is more curved than the pressure-sensitive adhesive sheet using the solvent-based pressure-sensitive adhesive. Tends to be inferior in sex.
「曲面貼付性」とは、曲面を有する被着体上に、感圧式接着シートを貼り付ける場合の適性を示す用語である。平面上に貼り付ける場合と異なり、曲面上に貼り付ける場合、感圧式接着シートの基材に曲面状態から平坦状態に復元しようとする応力が発生する。この応力は、被着体から感圧式接着シートが自ずと剥がれるように作用する。そのため、接着層の接着力が充分でないと、被着体に対して感圧式接着シートを貼り付けた後、ある程度の時間が経過すると、被着体から感圧式接着シートが自然に剥離してしまう恐れがある。
また、感圧式接着剤の接着力が充分に高いにもかかわらず、感圧式接着剤の凝集力が低すぎると、基材が平坦状に戻ろうとする応力に打ち勝てずに接着層の内部で破断が生じる、いわゆる「凝集破壊」が生じる恐れがある。凝集破壊が生じると、被着体側および感圧式接着シートの基材側の両方に感圧式接着剤が付着した状態で、感圧式接着シートが被着体から剥がれてしまう。
故に、曲面貼付性を良好にするには、感圧式接着剤の接着力と凝集力という2つの物性が好適である必要がある。
"Curved surface stickability" is a term indicating suitability for sticking a pressure-sensitive adhesive sheet on an adherend having a curved surface. Unlike the case of pasting on a flat surface, when pasting on a curved surface, stress is generated on the base material of the pressure-sensitive adhesive sheet to restore the curved surface state to the flat state. This stress acts so that the pressure-sensitive adhesive sheet naturally peels off from the adherend. Therefore, if the adhesive strength of the adhesive layer is not sufficient, the pressure-sensitive adhesive sheet will naturally peel off from the adherend after a certain period of time has passed after the pressure-sensitive adhesive sheet is attached to the adherend. There is a fear.
Further, even though the adhesive force of the pressure-sensitive adhesive is sufficiently high, if the cohesive force of the pressure-sensitive adhesive is too low, the substrate cannot overcome the stress of returning to a flat state and breaks inside the adhesive layer. May occur, so-called "cohesive failure". When cohesive failure occurs, the pressure-sensitive adhesive sheet is peeled off from the adherend with the pressure-sensitive adhesive adhered to both the adherend side and the base material side of the pressure-sensitive adhesive sheet.
Therefore, in order to improve the adhesiveness of the curved surface, it is necessary that the two physical properties of the pressure-sensitive adhesive, that is, the adhesive force and the cohesive force, are suitable.
水性感圧式接着剤の用途の拡大に伴い、水性型感圧式接着剤には、曲面貼付性が良好であることに加えて、高温環境下においても凝集力が高く、常温下および0℃以下の低温環境下においても、ポリエチレン等のポリオレフィン系樹脂等の低極性被着体を含む幅広い被着体に対して高い接着力を有することが求められるようになってきている。
なお、高温環境下における凝集力が高ければ、高温環境下において、被着体と感圧式接着シートとの間の位置ズレ等の接着不良を抑制することができる。高温環境下における被着体と感圧式接着シートとの間の良好な接着状態の保持は、「高温保持力」とも言う。
With the expansion of applications of water-based pressure-sensitive adhesives, water-based pressure-sensitive adhesives have good curved surface stickability and high cohesive force even in high-temperature environments, and are at room temperature and below 0 ° C. Even in a low temperature environment, it is required to have high adhesive strength to a wide range of adherends including low-polarity adherends such as polyolefin resins such as polyethylene.
If the cohesive force in a high temperature environment is high, it is possible to suppress poor adhesion such as positional deviation between the adherend and the pressure-sensitive adhesive sheet in a high temperature environment. Maintaining a good adhesive state between the adherend and the pressure-sensitive adhesive sheet in a high-temperature environment is also called "high-temperature holding force".
特許文献1には、ガラス転移温度(Tg)が−40℃未満である低Tgポリマーエマルション(A)と、ガラス転移温度(Tg)が−40℃〜0℃である高Tgポリマーエマルション(B)と、架橋剤(C)と、粘着付与樹脂(D)とを含むエマルション型粘着剤組成物が開示されている(請求項1)。
特許文献2には、ガラス転移温度(Tg)が−70℃〜−50℃の範囲にある水分散型アクリル系共重合体(ポリマーL)をベースポリマーとする水分散型の粘着剤組成物であって、固形分基準で、100質量部のポリマーLに対し、Tgが30〜120℃の範囲にある水分散型アクリル系共重合体(ポリマーH)0.5〜15質量部を含む、粘着剤組成物が開示されている(請求項1)。
この粘着剤組成物は、好ましくは、固形分基準で、100質量部のポリマーLに対して10〜40質量部の粘着付与樹脂をさらに含む(請求項7)。
The pressure-sensitive adhesive composition preferably further contains 10 to 40 parts by mass of a tack-imparting resin with respect to 100 parts by mass of the polymer L on a solid content basis (Claim 7).
特許文献3には、(メタ)アクリル酸アルキルエステルを主成分とするエチレン性不飽和単量体(A)および粘着付与剤(B)からなる油溶成分を、水媒体中で乳化剤を用いて、油溶成分の平均粒子径が1.0μm以下となるように乳化させた乳化液を重合して得られる樹脂エマルジョンの存在下に、さらに、(メタ)アクリル酸アルキルエステルを主成分とするエチレン性不飽和単量体(E)を重合してなるエマルジョン型粘着剤組成物が開示されている(請求項1)。
特許文献4には、
主成分として低Tgのアクリル系粘着剤エマルション(A)51〜90質量%と、副成分として高Tgの共重合体エマルション(B)10〜49質量%と含むエマルション型粘着剤組成物であって、
低Tgのアクリル系粘着剤エマルション(A)は、ガラス転移温度(Tg)が−70〜−50℃であり、
高Tgの共重合体エマルション(B)は、(メタ)アクリル酸アルキルエステル系単量体を含む単量体混合物100質量部に、20〜200質量部の粘着付与樹脂を存在させて乳化重合した共重合体のエマルションであり、該共重合体のガラス転移温度(Tg)が−30〜30℃である、エマルション型粘着剤組成物が開示されている(請求項1)。
なお、特許文献1〜4に記載の各成分の符号は、これら文献に記載の符号であり、本発明の各成分に使用する符号とは何ら関係がない。
In
An emulsion-type pressure-sensitive adhesive composition containing 51 to 90% by mass of a low Tg acrylic pressure-sensitive adhesive emulsion (A) as a main component and 10 to 49% by mass of a high Tg copolymer emulsion (B) as a sub-component. ,
The low Tg acrylic pressure-sensitive adhesive emulsion (A) has a glass transition temperature (Tg) of −70 to −50 ° C.
The high Tg copolymer emulsion (B) was emulsified and polymerized by allowing 20 to 200 parts by mass of a tackifier resin to be present in 100 parts by mass of a monomer mixture containing a (meth) acrylic acid alkyl ester-based monomer. An emulsion-type pressure-sensitive adhesive composition, which is an emulsion of a copolymer and has a glass transition temperature (Tg) of the copolymer of -30 to 30 ° C., is disclosed (claim 1).
The codes of the respective components described in
しかしながら、上記特許文献1〜4に記載の従来技術においては、良好な曲面貼付性、各種被着体に対する高い接着力、高温環境下における高い凝集力(高温保持力)、および低温環境下における高い接着力を全て達成することは難しい。特に、曲面貼付性と低温接着性は背反する特性であり、これらを両立することは難しい。
However, in the prior art described in
本発明の目的は、各種被着体に対する高い接着力と、良好な曲面貼付性と、高温環境下における高い凝集力(高温保持力)と、低温環境下における高い接着力とを有する水性感圧式接着剤とその製造方法、およびこれを用いた感圧式接着シートを提供することである。 An object of the present invention is a water-based pressure-sensitive type having high adhesive force to various adherends, good curved surface sticking property, high cohesive force (high temperature holding force) in a high temperature environment, and high adhesive force in a low temperature environment. An adhesive, a method for producing the same, and a pressure-sensitive adhesive sheet using the adhesive.
本発明の水性感圧式接着剤は、
ガラス転移温度(Tg)が相対的に低い第1のアクリル系共重合体(APL)を含む第1のアクリル系エマルション(AEL)と、
ガラス転移温度(Tg)が相対的に高い第2のアクリル系共重合体(APH)と粘着付与樹脂とを含む第2のアクリル系エマルション(AEH)とを含む水性感圧式接着剤であって、
第1のアクリル系共重合体(APL)のガラス転移温度が−70〜−40℃であり、
第2のアクリル系共重合体(APH)のガラス転移温度(Tg)が60〜120℃であり、
前記粘着付与樹脂は、軟化点が130℃以上のロジン系樹脂である、水性感圧式接着剤である。
The water-based pressure-sensitive adhesive of the present invention
A first acrylic emulsion (AEL) containing a first acrylic copolymer (APL) having a relatively low glass transition temperature (Tg),
A water-based pressure-sensitive adhesive containing a second acrylic copolymer (APH) having a relatively high glass transition temperature (Tg) and a second acrylic emulsion (AEH) containing a tackifier resin.
The glass transition temperature of the first acrylic copolymer (APL) is −70 to −40 ° C.
The glass transition temperature (Tg) of the second acrylic copolymer (APH) is 60 to 120 ° C.
The tackifier resin is a water-based pressure-sensitive adhesive which is a rosin-based resin having a softening point of 130 ° C. or higher.
本発明の水性感圧式接着剤の製造方法は、
ガラス転移温度(Tg)が相対的に低い第1のアクリル系共重合体(APL)を含む第1のアクリル系エマルション(AEL)と、
ガラス転移温度(Tg)が相対的に高い第2のアクリル系共重合体(APH)と粘着付与樹脂とを含む第2のアクリル系エマルション(AEH)とを含む水性感圧式接着剤の製造方法であって、
複数種のエチレン性不飽和単量体を乳化重合して、ガラス転移温度が−70〜−40℃である第1のアクリル系共重合体(APL)を含む第1のアクリル系エマルション(AEL)を製造する工程(1)と、
乳化剤と、軟化点が130℃以上のロジン系樹脂である粘着付与樹脂との存在下で、複数種のエチレン性不飽和単量体を乳化重合して、ガラス転移温度(Tg)が60〜120℃である第2のアクリル系共重合体(APH)を含む第2のアクリル系エマルション(AEH)を製造する工程(2)と、
第1のアクリル系エマルション(AEL)と第2のアクリル系エマルション(AEH)とを混合する工程(3)とを有するものである。
The method for producing a water-based pressure-sensitive adhesive of the present invention is
A first acrylic emulsion (AEL) containing a first acrylic copolymer (APL) having a relatively low glass transition temperature (Tg),
A method for producing an aqueous pressure-sensitive adhesive containing a second acrylic copolymer (APH) having a relatively high glass transition temperature (Tg) and a second acrylic emulsion (AEH) containing a tackifier resin. There,
A first acrylic emulsion (AEL) containing a first acrylic copolymer (APL) having a glass transition temperature of −70 to −40 ° C. by emulsion polymerization of a plurality of types of ethylenically unsaturated monomers. (1) and
In the presence of an emulsifier and a tackifier resin which is a rosin-based resin having a softening point of 130 ° C. or higher, a plurality of types of ethylenically unsaturated monomers are emulsion-polymerized to have a glass transition temperature (Tg) of 60 to 120. A step (2) of producing a second acrylic emulsion (AEH) containing a second acrylic copolymer (APH) at ° C.
It has a step (3) of mixing a first acrylic emulsion (AEL) and a second acrylic emulsion (AEH).
本発明の感圧式接着シートは、上記の本発明の水性感圧式接着剤の乾燥物からなる感圧式接着層を有するものである。 The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer made of a dried product of the above-mentioned water-based pressure-sensitive adhesive of the present invention.
本発明によれば、各種被着体に対する高い接着力と、良好な曲面貼付性と、高温環境下における高い凝集力(高温保持力)と、低温環境下における高い接着力とを有する水性感圧式接着剤とその製造方法、およびこれを用いた感圧式接着シートを提供することができる。
本発明の水性感圧式接着剤を用いて形成された感圧式接着層を含む感圧式接着シートは、被着体に貼付後、高温環境下でも、被着体と感圧式接着シートとの間の位置ズレ等の接着不良を抑制することができる。この感圧式接着シートは、曲面形状を有する被着体、および、一般的に接着が難しいポリオレフィン系樹脂等の低極性被着体に対しても、良好な接着力を有することができる。この感圧式接着シートは、低温環境下でも、一般的に接着が難しいポリオレフィン系樹脂等の低極性被着体に対しても、良好な接着力を有することができる。
According to the present invention, a water-based pressure-sensitive type having high adhesive force to various adherends, good curved surface sticking property, high cohesive force (high temperature holding force) in a high temperature environment, and high adhesive force in a low temperature environment. An adhesive, a method for producing the same, and a pressure-sensitive adhesive sheet using the same can be provided.
The pressure-sensitive adhesive sheet containing the pressure-sensitive adhesive layer formed by using the water-based pressure-sensitive adhesive of the present invention can be placed between the adherend and the pressure-sensitive adhesive sheet even in a high temperature environment after being attached to the adherend. Poor adhesion such as misalignment can be suppressed. This pressure-sensitive adhesive sheet can have good adhesive force even for an adherend having a curved surface shape and a low-polarity adherend such as a polyolefin resin which is generally difficult to adhere. This pressure-sensitive adhesive sheet can have good adhesive force even in a low temperature environment even for a low-polarity adherend such as a polyolefin resin, which is generally difficult to adhere.
以下、本発明の詳細を説明する。
本明細書において、特に断りのない限り、「単量体」はエチレン性不飽和単量体であり、(メタ)アクリル酸アルキルエステル単量体を含む、ラジカル重合可能なビニル基含有化合物の総称である。 本明細書において、特に断りのない限り、アクリル系共重合体のガラス転移温度(Tg)は、各原料単量体の単独重合体のTgを基に、FOXの式により理論的に求められる理論値である。単独重合体のTgについては、各種便覧および公知文献等に記載の周知の値を用いることができる。
The details of the present invention will be described below.
In the present specification, unless otherwise specified, the "monomer" is an ethylenically unsaturated monomer and is a general term for radically polymerizable vinyl group-containing compounds including a (meth) acrylic acid alkyl ester monomer. Is. In the present specification, unless otherwise specified, the glass transition temperature (Tg) of the acrylic copolymer is a theory theoretically obtained by the FOX formula based on the Tg of the homopolymer of each raw material monomer. The value. For Tg of the homopolymer, well-known values described in various handbooks and publicly known documents can be used.
[水性感圧式接着剤]
本発明の水性感圧式接着剤は、2種類のアクリル系エマルションを含む。具体的には、ガラス転移温度(Tg)が相対的に低い第1のアクリル系共重合体(APL)を含む第1のアクリル系エマルション(AEL)と、ガラス転移温度(Tg)が相対的に高い第2のアクリル系共重合体(APH)と粘着付与樹脂(TF)とを含む第2のアクリル系エマルション(AEH)とを含む。
[Aqueous pressure-sensitive adhesive]
The water-based pressure-sensitive adhesive of the present invention contains two types of acrylic emulsions. Specifically, the glass transition temperature (Tg) is relatively different from that of the first acrylic emulsion (AEL) containing the first acrylic copolymer (APL) having a relatively low glass transition temperature (Tg). It contains a second acrylic emulsion (AEH) containing a high second acrylic copolymer (APH) and a tackifier resin (TF).
本発明の水性感圧式接着剤は相分離構造を有し、第2のアクリル系共重合体(APH)と粘着付与樹脂(TF)とを含む相分離ドメインを含むことができる。
一般的に、Tgの低いアクリル系共重合体は、相対的に柔らかく、低温での接着力およびポリオレフィン系樹脂等の低極性被着体への接着力が高く、凝集力が低い傾向がある。一般的に、Tgの高いアクリル系共重合体は、相対的に硬く、特に低温での接着力が低く、凝集力が高い傾向がある。これら2種のアクリル系エマルションに対して粘着付与樹脂を単に添加するだけでは、ポリオレフィン系樹脂等の低極性被着体への接着力の向上および曲面接着性の向上のために、比較的多くの粘着付与樹脂が必要である。この場合、感圧式接着剤の柔軟性が損なわれ、低温接着力が低下する傾向がある。
本発明の水性感圧式接着剤では、Tgが相対的に高い第2のアクリル系共重合体(APH)と粘着付与樹脂(TF)とを含む相分離ドメインの形成によって、粘着付与樹脂(TF)の添加量を少なくしても、第2のアクリル系共重合体(APH)の硬さと接着力の低さを効果的に和らげることができる。
The water-based pressure-sensitive adhesive of the present invention has a phase-separated structure and can contain a phase-separated domain containing a second acrylic copolymer (APH) and a tackifier resin (TF).
In general, acrylic copolymers having a low Tg tend to be relatively soft, have high adhesive strength at low temperatures, and have high adhesive strength to low-polarity adherends such as polyolefin resins, and have low cohesive strength. In general, an acrylic copolymer having a high Tg tends to be relatively hard, has a low adhesive force particularly at a low temperature, and has a high cohesive force. By simply adding a tackifier resin to these two types of acrylic emulsions, a relatively large number of them are used to improve the adhesive force to low-polarity adherends such as polyolefin resins and the adhesiveness to curved surfaces. Adhesive-imparting resin is required. In this case, the flexibility of the pressure-sensitive adhesive is impaired, and the low-temperature adhesive force tends to decrease.
In the water-based pressure-sensitive adhesive of the present invention, the pressure-sensitive adhesive resin (TF) is formed by forming a phase-separated domain containing a second acrylic copolymer (APH) having a relatively high Tg and a pressure-sensitive adhesive resin (TF). Even if the amount of the second acrylic copolymer (APH) added is small, the hardness and low adhesive strength of the second acrylic copolymer (APH) can be effectively alleviated.
相分離の有無または相分離状態は、水性感圧式接着剤または水性感圧式接着剤の乾燥物からなる感圧式接着層の走査型プローブ顕微鏡観察により確認することができる。
相分離の有無または相分離状態はまた、本発明の水性感圧式接着剤の乾燥物からなる感圧式接着層のヘーズ値を指標に評価することができる。50μm厚のポリエチレンテレフタレート(PET)フィルム上に、乾燥質量25g/m2の条件で水性感圧式接着剤を塗工および乾燥して得られる積層体のヘーズ値は、好ましくは5.0〜10.0、より好ましくは6.0〜8.0である。上記積層体のヘーズ値が5.0以上であれば、感圧式接着層に明確に相分離が見られ、10.0を超えると、感圧式接着層に相分離が明確に見られるものの感圧式接着層の柔軟性が低下する傾向があり、好ましくない。上記積層体のヘーズ値が6.0〜10.0であれば、感圧式接着層の相分離と柔軟性のバランスが良好となる。
Tgが低く相対的に柔らかい第1のアクリル系共重合体(APL)を含むマトリクス相(海相)の中に、Tgが高く相対的に硬い第2のアクリル系共重合体(APH)と粘着付与樹脂(TF)とを含む相分離ドメイン(島相)が複数形成されることで、低温接着力、曲面接着性、ポリオレフィン系樹脂等の低極性被着体への接着力、および高温環境下での凝集力(高温保持力)のバランスが良好となる。
The presence or absence of phase separation or the phase separation state can be confirmed by observing a scanning probe microscope of a pressure-sensitive adhesive layer made of a water-based pressure-sensitive adhesive or a dried product of the water-based pressure-sensitive adhesive.
The presence or absence of phase separation or the phase separation state can also be evaluated using the haze value of the pressure-sensitive adhesive layer made of the dried product of the water-based pressure-sensitive adhesive of the present invention as an index. The haze value of the laminate obtained by applying and drying a water-based pressure-sensitive adhesive on a 50 μm-thick polyethylene terephthalate (PET) film under the condition of a dry mass of 25 g / m 2 is preferably 5.0 to 10. It is 0, more preferably 6.0 to 8.0. If the haze value of the laminate is 5.0 or more, phase separation is clearly seen in the pressure-sensitive adhesive layer, and if it exceeds 10.0, phase separation is clearly seen in the pressure-sensitive adhesive layer, but the pressure-sensitive type. The flexibility of the adhesive layer tends to decrease, which is not preferable. When the haze value of the laminated body is 6.0 to 10.0, the balance between the phase separation and the flexibility of the pressure-sensitive adhesive layer is good.
Adhesive to the second acrylic copolymer (APH), which has a high Tg and is relatively hard, in the matrix phase (sea phase) containing the first acrylic copolymer (APL), which has a low Tg and is relatively soft. By forming a plurality of phase-separated domains (island phases) including the imparting resin (TF), low-temperature adhesive strength, curved surface adhesiveness, adhesive strength to low-polarity adherends such as polyolefin resins, and high temperature environment The balance of cohesive force (high temperature holding force) is good.
本発明の水性感圧式接着剤は、上記2種類のアクリル系エマルションを含むことで、各種被着体に対する高い接着力と、良好な曲面貼付性と、高温環境下における高い凝集力(高温保持力)と、低温環境下における高い接着力とを有することができる。
本発明の水性感圧式接着剤を用いて形成された感圧式接着層を含む感圧式接着シートは、被着体に貼付後、高温環境下でも、被着体と感圧式接着シートとの間の位置ズレ等の接着不良を抑制することができる。この感圧式接着シートは、曲面形状を有する被着体、および、一般的に接着が難しいポリオレフィン系樹脂等の低極性被着体に対しても、良好な接着力を有することができる。この感圧式接着シートは、低温環境下でも、一般的に接着が難しいポリオレフィン系樹脂等の低極性被着体に対しても、良好な接着力を有することができる。
The water-based pressure-sensitive adhesive of the present invention contains the above two types of acrylic emulsions, so that it has high adhesive force to various adherends, good curved surface adhesiveness, and high cohesive force (high temperature holding power) in a high temperature environment. ) And high adhesive strength in a low temperature environment.
The pressure-sensitive adhesive sheet containing the pressure-sensitive adhesive layer formed by using the water-based pressure-sensitive adhesive of the present invention can be placed between the adherend and the pressure-sensitive adhesive sheet even in a high temperature environment after being attached to the adherend. Poor adhesion such as misalignment can be suppressed. This pressure-sensitive adhesive sheet can have good adhesive force even for an adherend having a curved surface shape and a low-polarity adherend such as a polyolefin resin which is generally difficult to adhere. This pressure-sensitive adhesive sheet can have good adhesive force even in a low temperature environment even for a low-polarity adherend such as a polyolefin resin, which is generally difficult to adhere.
「高温環境」とは常温(20〜25℃)よりも高い温度環境であり、例えば、60〜90℃の温度環境である。
「低温環境」とは常温(20〜25℃)よりも低い温度環境であり、例えば、−25〜5℃の温度環境である。
The "high temperature environment" is a temperature environment higher than normal temperature (20 to 25 ° C.), for example, a temperature environment of 60 to 90 ° C.
The "low temperature environment" is a temperature environment lower than normal temperature (20 to 25 ° C.), for example, a temperature environment of 25 to 5 ° C.
粘着付与樹脂(TF)の軟化点は、好ましくは100℃以上、より好ましくは120℃以上、特に好ましくは130℃以上、最も好ましくは150℃以上である。
粘着付与樹脂(TF)の軟化点が高いほど、好ましくは130℃以上であることで、これを含む接着剤の凝集力を効果的に高めることができ、より少量の使用で、各種被着体に対する高い接着力と、良好な曲面貼付性と、高温環境下における高い凝集力(高温保持力)と、低温環境下における高い接着力とを有することができる。
The softening point of the tackifier resin (TF) is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, particularly preferably 130 ° C. or higher, and most preferably 150 ° C. or higher.
The higher the softening point of the tackifier resin (TF), the more preferably 130 ° C. or higher, so that the cohesive force of the adhesive containing the adhesive can be effectively increased, and various adherends can be used with a smaller amount. It can have a high adhesive force against, good curved surface sticking property, a high cohesive force (high temperature holding force) in a high temperature environment, and a high adhesive force in a low temperature environment.
粘着付与樹脂(TF)の重量平均分子量(Mw)は特に制限されず、好ましくは1700〜4500、より好ましくは2800〜4000である。粘着付与樹脂(TF)のMwが上記範囲内であれば、これを含む接着剤の凝集力を効果的に高めることができ、より少量の使用で、各種被着体に対する高い接着力と、良好な曲面貼付性と、高温環境下における高い凝集力(高温保持力)と、低温環境下における高い接着力とを有することができる。
本明細書において、特に断りのない限り「重量平均分子量(Mw)」はゲル浸透クロマトグラフィ(GPC)法により求められるポリスチレン換算の重量平均分子量である。
The weight average molecular weight (Mw) of the tackifier resin (TF) is not particularly limited, and is preferably 1700 to 4500, more preferably 2800 to 4000. If the Mw of the tackifier resin (TF) is within the above range, the cohesive force of the adhesive containing the adhesive can be effectively increased, and with a smaller amount of use, the adhesive force to various adherends is high and good. It can have a smooth curved surface sticking property, a high cohesive force (high temperature holding power) in a high temperature environment, and a high adhesive force in a low temperature environment.
In the present specification, unless otherwise specified, "weight average molecular weight (Mw)" is a polystyrene-equivalent weight average molecular weight determined by a gel permeation chromatography (GPC) method.
上記したように、本発明の水性感圧式接着剤では、粘着付与樹脂(TF)の使用量を少量とすることができる。粘着付与樹脂(TF)の使用量が少量でよいので、原料コスト低減、高温環境下における高い凝集力(高温保持力)、低温接着力、および感圧接着剤の低黄変性の観点から、好ましい。
従来一般的なアクリル系水性感圧式接着剤では、アクリル系共重合体の総量100質量部に対して、粘着付与樹脂の含有量は6質量部超である。
本発明の水性感圧式接着剤では、例えば、第1のアクリル系共重合体(APL)と第2のアクリル系共重合体(APH)との総量100質量部に対して、粘着付与樹脂(TF)の含有量は1.0質量部以上5.5質量部未満とすることができる。粘着付与樹脂(TF)の含有量は、好ましくは5.0質量部以下、より好ましくは4.5質量部以下、特に好ましくは4.0質量部以下である。粘着付与樹脂(TF)の含有量は、好ましくは1.5質量部以上である。
As described above, in the water-based pressure-sensitive adhesive of the present invention, the amount of the tackifier resin (TF) used can be small. Since the amount of the tackifier resin (TF) used may be small, it is preferable from the viewpoints of reducing the cost of raw materials, high cohesive force (high temperature holding power) in a high temperature environment, low temperature adhesive force, and low yellowing of the pressure-sensitive adhesive. ..
In the conventional general acrylic water-based pressure-sensitive adhesive, the content of the tackifier resin is more than 6 parts by mass with respect to 100 parts by mass of the total amount of the acrylic copolymer.
In the water-based pressure-sensitive adhesive of the present invention, for example, the tackifier resin (TF) is applied to 100 parts by mass of the total amount of the first acrylic copolymer (APL) and the second acrylic copolymer (APH). ) Can be 1.0 part by mass or more and less than 5.5 parts by mass. The content of the tackifier resin (TF) is preferably 5.0 parts by mass or less, more preferably 4.5 parts by mass or less, and particularly preferably 4.0 parts by mass or less. The content of the tackifier resin (TF) is preferably 1.5 parts by mass or more.
本発明の水性感圧式接着剤において、第1のアクリル系共重合体(APL)と第2のアクリル系共重合体(APH)との総量100質量部に対して、第1のアクリル系共重合体(APL)の含有量が80〜95質量部であり、第2のアクリル系共重合体(APH)の含有量が20〜5質量部であることが好ましい。
第1のアクリル系共重合体(APL)の含有量が上記範囲にあることで、ポリオレフィン系樹脂等の低極性被着体への接着力および低温接着性が優れたものとなる。第2のアクリル系共重合体(APH)の含有量が上記範囲にあることで、曲面貼付性と高温環境下における高い凝集力(高温保持力)の両立が可能となる。
第1のアクリル系共重合体(APL)と第2のアクリル系共重合体(APH)との総量100質量部に対して、第1のアクリル系共重合体(APL)の含有量が87〜92質量部であり、第2のアクリル系共重合体(APH)の含有量が13〜8質量部であることがより好ましい。
In the water-based pressure-sensitive adhesive of the present invention, the first acrylic copolymer weight is relative to 100 parts by mass of the total amount of the first acrylic copolymer (APL) and the second acrylic copolymer (APH). The content of the coalescence (APL) is preferably 80 to 95 parts by mass, and the content of the second acrylic copolymer (APH) is preferably 20 to 5 parts by mass.
When the content of the first acrylic copolymer (APL) is within the above range, the adhesive strength to a low-polarity adherend such as a polyolefin resin and the low-temperature adhesiveness are excellent. When the content of the second acrylic copolymer (APH) is within the above range, it is possible to achieve both curved surface stickability and high cohesive force (high temperature holding force) in a high temperature environment.
The content of the first acrylic copolymer (APL) is 87 to 87 to 100 parts by mass of the total amount of the first acrylic copolymer (APL) and the second acrylic copolymer (APH). It is more preferably 92 parts by mass and the content of the second acrylic copolymer (APH) is 13 to 8 parts by mass.
(第1のアクリル系エマルション(AEL))
第1のアクリル系エマルション(AEL)は、ガラス転移温度(Tg)が相対的に低い第1のアクリル系共重合体(APL)を含む。第1のアクリル系共重合体(APL)のTgは、−70〜−40℃である。このエマルションは、本発明の水性感圧式接着剤の主成分であり、基本的な粘着性能の発現に寄与する。第1のアクリル系エマルション(AEL)は、1種または2種以上用いることができる。
(First acrylic emulsion (AEL))
The first acrylic emulsion (AEL) contains a first acrylic copolymer (APL) having a relatively low glass transition temperature (Tg). The Tg of the first acrylic copolymer (APL) is −70 to −40 ° C. This emulsion is the main component of the water-based pressure-sensitive adhesive of the present invention and contributes to the development of basic adhesive performance. The first acrylic emulsion (AEL) can be used alone or in combination of two or more.
第1のアクリル系エマルション(AEL)は、公知の乳化重合法により製造でき、乳化剤の存在下で、複数種のエチレン性不飽和単量体を含むエチレン性不飽和単量体混合物(AML)を乳化重合して得られる。
第1のアクリル系共重合体(APL)のTgが−70〜−40℃の範囲内となるように、原料の複数種のエチレン性不飽和単量体を選定し、重合条件を決定する。第1のアクリル系共重合体(APL)のTgが−70℃未満では、被着体、特にポリオレフィン系樹脂等の低極性被着体への接着力、および曲面貼り付け性が不充分となる恐れがある。Tgが−40℃を超えると、タック感の低下を招き、接着力(特に低温接着力)の低下を招く恐れがある。Tgは、より好ましくは−65〜−50℃、特に好ましくは−60〜−45℃である。
The first acrylic emulsion (AEL) can be produced by a known emulsion polymerization method, and in the presence of an emulsifier, an ethylenically unsaturated monomer mixture (AML) containing a plurality of kinds of ethylenically unsaturated monomers can be prepared. Obtained by emulsion polymerization.
A plurality of types of ethylenically unsaturated monomers as raw materials are selected so that the Tg of the first acrylic copolymer (APL) is in the range of −70 to −40 ° C., and the polymerization conditions are determined. If the Tg of the first acrylic copolymer (APL) is less than −70 ° C., the adhesive strength to the adherend, particularly to a low-polarity adherend such as a polyolefin resin, and the adhesiveness to a curved surface become insufficient. There is a fear. If Tg exceeds −40 ° C., the tack feeling may be lowered and the adhesive strength (particularly low temperature adhesive strength) may be lowered. Tg is more preferably −65 to −50 ° C., particularly preferably −60 to −45 ° C.
<エチレン性不飽和単量体混合物(AML)>
第1のアクリル系エマルション(AEL)は、エチレン性不飽和単量体混合物(AML)の乳化重合物である。
エチレン性不飽和単量体混合物(AML)は、直鎖または分岐鎖のアルコールと(メタ)アクリル酸とのエステルである1種以上の(メタ)アクリル酸アルキルエステルを含み、必要に応じて、1種以上の他の単量体を含むことができる。
<Ethylene unsaturated monomer mixture (AML)>
The first acrylic emulsion (AEL) is an emulsion polymer of an ethylenically unsaturated monomer mixture (AML).
The ethylenically unsaturated monomeric mixture (AML) comprises one or more (meth) acrylic acid alkyl esters, which are esters of linear or branched alcohols with (meth) acrylic acid, and optionally. It can contain one or more other monomers.
(メタ)アクリル酸アルキルエステルとしては、例えば、メチル(メタ)アクリレート、エチル(メタ)アクリレート、プロピル(メタ)アクリレート、ブチル(メタ)アクリレート、ヘキシル(メタ)アクリレート、n−オクチル(メタ)アクリレート、2−エチルヘキシル(メタ)アクリレート、ラウリル(メタ)アクリレート、ミリスチル(メタ)アクリレート、およびステアリルアクリレート等が挙げられる。これらは、1種または2種以上用いることができる。
中でも、アルキル基の炭素数が1〜14である(メタ)アクリル酸アルキルエステルを用いることが、水性感圧式接着剤のタック感向上および接着力向上のために好ましい。
エチレン性不飽和単量体混合物(AML)は、ブチルアクリレート(BA)を含むことが好ましく、ブチルアクリレート(BA)と2−エチルヘキシルアクリレート(2−EHA)とを含むことがより好ましい。
エチレン性不飽和単量体混合物(AML)中の(メタ)アクリル酸アルキルエステルの含有量は、好ましくは40.0〜99.5質量%、好ましくは40.0〜98.0質量%、より好ましくは90〜99質量%である。特に、ブチルアクリレートの含有量が40〜98質量%である場合、良好な曲面貼付性と良好な接着力とを両立することができるために好ましい。
Examples of the (meth) acrylic acid alkyl ester include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, and n-octyl (meth) acrylate. Examples thereof include 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, myristyl (meth) acrylate, and stearyl acrylate. These can be used alone or in combination of two or more.
Above all, it is preferable to use a (meth) acrylic acid alkyl ester having an alkyl group having 1 to 14 carbon atoms in order to improve the tackiness and the adhesive strength of the water-based pressure-sensitive adhesive.
The ethylenically unsaturated monomer mixture (AML) preferably contains butyl acrylate (BA), and more preferably contains butyl acrylate (BA) and 2-ethylhexyl acrylate (2-EHA).
The content of the (meth) acrylic acid alkyl ester in the ethylenically unsaturated monomer mixture (AML) is preferably 40.0 to 99.5% by mass, preferably 40.0 to 98.0% by mass, and more. It is preferably 90 to 99% by mass. In particular, when the content of butyl acrylate is 40 to 98% by mass, it is preferable because good curved surface stickability and good adhesive strength can be achieved at the same time.
他の単量体としては、カルボキシ基を有するエチレン性不飽和単量体、水酸基を有するエチレン性不飽和単量体、アマイド結合を有するエチレン性不飽和単量体、スチレン系不飽和単量体、およびビニル化合物等が挙げられる。 Other monomers include an ethylenically unsaturated monomer having a carboxy group, an ethylenically unsaturated monomer having a hydroxyl group, an ethylenically unsaturated monomer having an amide bond, and a styrene-based unsaturated monomer. , And vinyl compounds and the like.
カルボキシ基を有するエチレン性不飽和単量体としては、例えば、(メタ)アクリル酸、(メタ)アクリル酸カルボキシエチル、マレイン酸、フマル酸、およびイタコン酸等が挙げられる。これらは、1種または2種以上用いることができる。中でも、エマルションの安定性の観点から、(メタ)アクリル酸が好ましい。
エチレン性不飽和単量体混合物(AEL)中のカルボキシ基を有するエチレン性不飽和単量体の含有量は、好ましくは0.5〜2.0質量%である。含有量がこの範囲内にあることで、合成時の凝集物の発生が抑制され、中和後のハンドリングの良好なエマルションが得られやすい。
紙等の被着体に対して感圧式接着シートを貼付した状態での経時劣化を抑制する観点から、エチレン性不飽和単量体混合物(AML)中の酸基を有する1種以上の単量体の総量は、好ましくは1.0質量%以下である。
Examples of the ethylenically unsaturated monomer having a carboxy group include (meth) acrylic acid, carboxyethyl (meth) acrylic acid, maleic acid, fumaric acid, and itaconic acid. These can be used alone or in combination of two or more. Of these, (meth) acrylic acid is preferable from the viewpoint of emulsion stability.
The content of the ethylenically unsaturated monomer having a carboxy group in the ethylenically unsaturated monomer mixture (AEL) is preferably 0.5 to 2.0% by mass. When the content is within this range, the generation of agglomerates during synthesis is suppressed, and an emulsion with good handling after neutralization can be easily obtained.
One or more single amounts having an acid group in an ethylenically unsaturated monomer mixture (AML) from the viewpoint of suppressing deterioration over time when a pressure-sensitive adhesive sheet is attached to an adherend such as paper. The total amount of the body is preferably 1.0% by mass or less.
水酸基を有するエチレン性不飽和単量体としては、例えば、ヒドロキシエチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、およびヒドロキシブチル(メタ)アクリレート等が挙げられる。これらは、1種または2種以上用いることができる。
エチレン性不飽和単量体混合物(AML)が水酸基を有するエチレン性不飽和単量体を含む場合、エチレン性不飽和単量体混合物(AML)中の水酸基を有するエチレン性不飽和単量体の含有量は、好ましくは2〜10質量%、より好ましくは3質量%以上6質量%未満である。この場合、曲面貼付性をより向上することができる。
Examples of the ethylenically unsaturated monomer having a hydroxyl group include hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, and hydroxybutyl (meth) acrylate. These can be used alone or in combination of two or more.
When the ethylenically unsaturated monomer mixture (AML) contains an ethylenically unsaturated monomer having a hydroxyl group, the ethylenically unsaturated monomer having a hydroxyl group in the ethylenically unsaturated monomer mixture (AML) The content is preferably 2 to 10% by mass, more preferably 3% by mass or more and less than 6% by mass. In this case, the adhesiveness of the curved surface can be further improved.
アマイド結合を有するエチレン性不飽和単量体としては、例えば、(メタ)アクリルアミド、およびジアセトン(メタ)アクリルアミド等が挙げられる。これらは、1種または2種以上用いることができる。 Examples of the ethylenically unsaturated monomer having an amide bond include (meth) acrylamide and diacetone (meth) acrylamide. These can be used alone or in combination of two or more.
スチレン系不飽和単量体としては、例えば、スチレン;2−メチルスチレン、3−メチルスチレン、4−メチルスチレン、4−エチルスチレン、及び4−tert−ブチルスチレン等の核アルキル置換スチレン;α−メチルスチレン、及び4−メチル−α−メチルスチレン等のα−アルキル置換スチレン等が挙げられる。これらは、1種または2種以上用いることができる。 Examples of the styrene-based unsaturated monomer include styrene; nuclear alkyl-substituted styrenes such as 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-ethylstyrene, and 4-tert-butylstyrene; α-. Examples thereof include methyl styrene and α-alkyl substituted styrene such as 4-methyl-α-methyl styrene. These can be used alone or in combination of two or more.
本発明の効果を損なわない範囲で、上記以外のその他のエチレン性不飽和単量体を用いることができる。その他のエチレン性不飽和単量体としては、例えば、メトキシエチル(メタ)アクリレート、アセトアセトキシエチル(メタ)アクリレート、N,N−ジメチルアミノエチル(メタ)アクリレート、N,N−ジエチルアミノエチル(メタ)アクリレート、ビニルピロリドン、ビニルピリジン、酢酸ビニル、プロピオン酸ビニル、スチレン、(メタ)アクリロニトリル、ブタジエン、およびクロロプレン等が挙げられる。これらは、1種または2種以上用いることができる。 Other ethylenically unsaturated monomers other than the above can be used as long as the effects of the present invention are not impaired. Examples of other ethylenically unsaturated monomers include methoxyethyl (meth) acrylate, acetoacetoxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, and N, N-diethylaminoethyl (meth). Acrylate, vinylpyrrolidone, vinylpyridine, vinyl acetate, vinyl propionate, styrene, (meth) acrylonitrile, butadiene, chloroprene and the like can be mentioned. These can be used alone or in combination of two or more.
<乳化剤>
第1のアクリル系エマルション(AEL)の合成に用いる乳化剤としては、公知の反応性または非反応性の乳化剤を用いることができる。乳化剤は、1種または2種以上用いることができる。
<Emulsifier>
As the emulsifier used for the synthesis of the first acrylic emulsion (AEL), a known reactive or non-reactive emulsifier can be used. One type or two or more types of emulsifiers can be used.
反応性乳化剤の例示は、以下の通りである。
アニオン系乳化剤としては、ノニルフェニル骨格のアニオン系乳化剤(ADEKA社製「アデカリアソープSE−10N」、および第一工業製薬社製「アクアロンHS−10、HS−20」等)、長鎖アルキル骨格のアニオン系乳化剤(第一工業製薬社製「アクアロンKH−05、KH−10」、およびADEKA社製「アデカリアソープSR−10N」等)、燐酸エステル骨格のアニオン系乳化剤(日本化薬社製「KAYARAD」等)が例示できる。
ノニオン系乳化剤としては、ポリオキシエチレンアルキルエーテル類、ポリオキシエチレンアルキルフェニルエーテル類、ソルビタン高級脂肪酸エステル類、およびグリセリン高級脂肪酸エステル類等が挙げられる。これらノニオン系乳化剤は、分子の末端あるいは中間部に不飽和二重結合を有し、単量体と共重合可能なものである。市販のノニオン系乳化剤としては、ADEKA社製「アデカリアソープNE−10」、第一工業製薬社製「アクアロンRN−10、RN −20、RN−50」、および日本乳化剤社製「アントックスNA−16」等が例示できる。
Examples of reactive emulsifiers are as follows.
Examples of anionic emulsifiers include nonylphenyl skeleton anionic emulsifiers (ADEKA's "ADEKA RIA SOLP SE-10N", Daiichi Kogyo Seiyaku Co., Ltd. "Aqualon HS-10, HS-20", etc.) and long-chain alkyl skeletons. Anionic emulsifiers (Aquaron KH-05, KH-10 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., ADEKA "Adecaria Soap SR-10N", etc.), anionic emulsifiers with phosphoric acid ester skeleton (manufactured by Nippon Kayaku Co., Ltd.) "KAYARAD" etc.) can be exemplified.
Examples of the nonionic emulsifier include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, sorbitan higher fatty acid esters, glycerin higher fatty acid esters and the like. These nonionic emulsifiers have an unsaturated double bond at the terminal or intermediate portion of the molecule and can be copolymerized with a monomer. Commercially available nonionic emulsifiers include "ADEKA Adecaria Soap NE-10" manufactured by ADEKA, "Aqualon RN-10, RN-20, RN-50" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., and "Antox NA" manufactured by Nippon Emulsifier Co., Ltd. -16 ”and the like can be exemplified.
非反応性乳化剤の例示は、以下の通りである。
アニオン系乳化剤としては、ステアリン酸ナトリウム等の高級脂肪酸塩類;ドデシルベンゼンスルホン酸ナトリウム等のアルキルアリールスルホン酸塩類;ラウリル硫酸ナトリウム等のアルキル硫酸エステル塩類;ポリオキシエチレンラウリルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルエーテル硫酸エステル塩類;ポリオキシエチレンノニルフェニルエーテル硫酸ナトリウム等のポリオキシエチレンアルキルアリールエーテル硫酸エステル塩類等が例示できる。
ノニオン系乳化剤としては、ポリオキシエチレンラウリルエーテル等のポリオキシエチレンアルキルエーテル類;ポリオキシエチレンノニルフェニルエーテル等のポリオキシエチレンアルキルフェニルエーテル類;ソルビタンモノステアレート等のソルビタン高級脂肪酸エステル類;オレイン酸モノグリセライド等のグリセリン高級脂肪酸エステル類等が例示できる。
Examples of non-reactive emulsifiers are as follows.
Examples of anionic emulsifiers include higher fatty acid salts such as sodium stearate; alkylaryl sulfonates such as sodium dodecylbenzene sulfonate; alkyl sulfate esters such as sodium lauryl sulfate; polyoxyethylene polyoxyethylene such as sodium lauryl ether sulfate. Alkyl ether sulfate ester salts; Examples thereof include polyoxyethylene alkylaryl ether sulfate ester salts such as polyoxyethylene nonylphenyl ether sulfate sodium.
Nonionic emulsifiers include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether; polyoxyethylene alkyl phenyl ethers such as polyoxyethylene nonylphenyl ether; sorbitan higher fatty acid esters such as sorbitan monostearate; oleic acid. Examples thereof include glycerin higher fatty acid esters such as monoglyceride.
<重合開始剤>
第1のアクリル系エマルション(AEL)の合成に用いる重合開始剤としては、例えば、過硫酸カリウムおよび過硫酸アンモニウム等の過硫酸塩;アゾビス系カチオン塩;水酸基付加物質等の水溶性の熱分解型重合触媒;レドックス系重合触媒を用いることができる。
レドックス系重合触媒としては、例えば、t−ブチルハイドロパーオキサイド、ベンゾイルパーオキサイド、およびクメンハイドロパーオキサイド等の有機過酸化物と、ロンガリットおよび/またはメタ重亜硫酸ナトリウム等の還元剤との組合せ;過硫酸カリウムおよび過硫酸アンモニウム等の過酸化物と、ロンガリットおよび/またはチオ硫酸ナトリウム等との組合せ;過酸化水素水とアスコルビン酸との組合せ等が挙げられる。
<Polymerization initiator>
Examples of the polymerization initiator used for the synthesis of the first acrylic emulsion (AEL) include persulfates such as potassium persulfate and ammonium persulfate; azobis-based cationic salts; and water-soluble thermal decomposition type polymerizations such as hydroxyl group addition substances. Catalyst: A redox-based polymerization catalyst can be used.
Examples of the redox-based polymerization catalyst include a combination of an organic peroxide such as t-butyl hydroperoxide, benzoyl peroxide, and cumene hydroperoxide and a reducing agent such as longalite and / or sodium metabisulfite; Combinations of peroxides such as potassium sulfate and ammonium persulfate with longalite and / or sodium thiosulfate; combinations of hydrogen peroxide solution and ascorbic acid and the like can be mentioned.
<連鎖移動剤>
第1のアクリル系エマルション(AEL)の合成には、第1のアクリル系共重合体(APL)の分子量および/または分子量分布を制御するために、メルカプタン系、チオグリコール系、およびβ−メルカプトプロピオン酸等のチオール系化合物等の連鎖移動剤を用いることができる。その使用量は、エチレン性不飽和単量体混合物(AEL)100質量部に対して、好ましくは0.01〜1.0質量部である。
<Chain transfer agent>
For the synthesis of the first acrylic emulsion (AEL), mercaptans, thioglycols, and β-mercaptopropions are used to control the molecular weight and / or molecular weight distribution of the first acrylic copolymer (APL). A chain transfer agent such as a thiol-based compound such as an acid can be used. The amount used is preferably 0.01 to 1.0 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer mixture (AEL).
(第1のアクリル系エマルション(AEL)の製造方法)
ガラス転移温度(Tg)が−70〜−40℃である第1のアクリル系共重合体(APL)を含む第1のアクリル系エマルション(AEL)は、複数種のエチレン性不飽和単量体を含むエチレン性不飽和単量体混合物(AML)を乳化重合することで得られる(工程(1))。
乳化重合では、複数種のエチレン性不飽和単量体の混合物を、乳化剤および重合開始剤を用い、水性媒体中で重合する。
(Method for Producing First Acrylic Emulsion (AEL))
The first acrylic emulsion (AEL) containing the first acrylic copolymer (APL) having a glass transition temperature (Tg) of −70 to −40 ° C. contains a plurality of types of ethylenically unsaturated monomers. It is obtained by emulsion polymerization of an ethylenically unsaturated monomer mixture (AML) containing the mixture (step (1)).
In emulsion polymerization, a mixture of a plurality of types of ethylenically unsaturated monomers is polymerized in an aqueous medium using an emulsifier and a polymerization initiator.
まず、複数種のエチレン性不飽和単量体を混合し、均一な単量体混合溶液(エチレン性不飽和単量体混合物(AML))を得る。必要に応じて、この混合溶液に水および乳化剤の一部または全量を加えて混合して、乳化液を得てもよい。
上記の混合溶液(エチレン性不飽和単量体混合物(AML))またはこれを含む乳化液を重合の原料液として用い、重合開始剤の存在下で重合を行う。この際、原料液の全量を反応容器に仕込んで重合を開始してもよいし、原料液の一部を反応容器に仕込んで重合を開始した後に残りの原料液を1回でまたは複数回に分けて添加してもよいし、原料液の一部を反応容器に仕込んで重合を開始した後に残りの原料液を連続滴下してもよいし、あらかじめ水の一部または全量および必要に応じて乳化剤の一部または全量を反応容器に仕込んでおき、原料液の全量を連続滴下してもよい。
原料液として単量体混合溶液(エチレン性不飽和単量体混合物(AML))を用いる場合には、あらかじめ反応容器に乳化剤の全量および水の一部または全量を仕込んでおくことが好ましい。
First, a plurality of types of ethylenically unsaturated monomers are mixed to obtain a uniform monomer mixed solution (ethylene unsaturated monomer mixture (AML)). If necessary, water and a part or all of the emulsifier may be added to this mixed solution and mixed to obtain an emulsion.
The above mixed solution (ethylene unsaturated monomer mixture (AML)) or an emulsion containing the above mixed solution is used as a raw material solution for polymerization, and polymerization is carried out in the presence of a polymerization initiator. At this time, the whole amount of the raw material liquid may be charged into the reaction vessel to start the polymerization, or a part of the raw material liquid may be charged into the reaction vessel to start the polymerization, and then the remaining raw material liquid may be charged once or multiple times. It may be added separately, or a part of the raw material liquid may be charged in a reaction vessel to start polymerization and then the remaining raw material liquid may be continuously added dropwise, or a part or all of the water and, if necessary, may be added in advance. A part or all of the emulsifier may be charged in the reaction vessel, and the whole amount of the raw material liquid may be continuously added dropwise.
When a monomer mixed solution (ethylenically unsaturated monomer mixture (AML)) is used as the raw material liquid, it is preferable to charge the reaction vessel in advance with the entire amount of the emulsifier and a part or the whole amount of water.
重合開始剤は、あらかじめ全量を反応容器に仕込んでおいてもよいし、昇温後に全量を添加してもよいし、一部を反応容器に仕込んでおき重合を開始した後に残りを1回でまたは複数回に分けて添加してもよいし、一部を反応容器に仕込んでおき重合を開始した後に残りを連続滴下してもよいし、全量を連続滴下してもよい。
重合開始剤を分割添加または連続滴下する場合には、重合開始剤単独で反応容器内に分割添加または連続滴下してもよいし、原料液と混合した状態で分割添加または連続滴下してもよい。なお、上記手法により重合開始剤を添加した後、反応率を高める目的で、さらに1回または2回以上重合開始剤を追加添加してもよい。
The entire amount of the polymerization initiator may be charged in the reaction vessel in advance, the entire amount may be added after the temperature is raised, or a part of the polymerization initiator may be charged in the reaction vessel and the rest may be charged once after the polymerization is started. Alternatively, it may be added in a plurality of times, a part thereof may be charged in a reaction vessel and the polymerization may be started, and then the rest may be continuously added dropwise, or the entire amount may be continuously added dropwise.
When the polymerization initiator is added separately or continuously added dropwise, the polymerization initiator may be added separately or continuously added dropwise into the reaction vessel, or may be added separately or continuously added dropwise in a state of being mixed with the raw material solution. .. After adding the polymerization initiator by the above method, the polymerization initiator may be additionally added once or twice or more for the purpose of increasing the reaction rate.
重合時には、pH調整のため、pH緩衝剤を使用してもよい。
カルボキシ基を有する単量体を使用する場合、得られた共重合体に含まれるカルボキシ基の一部または全部を、アンモニア、有機アミン、水酸化カリウム、クエン酸ナトリウム、および水酸化ナトリウム等の塩基性化合物を用いて中和してもよい。
At the time of polymerization, a pH buffer may be used to adjust the pH.
When a monomer having a carboxy group is used, a part or all of the carboxy group contained in the obtained copolymer is used as a base such as ammonia, an organic amine, potassium hydroxide, sodium citrate, and sodium hydroxide. It may be neutralized with a sex compound.
(第2のアクリル系エマルション(AEH))
第2のアクリル系エマルション(AEH)は、ガラス転移温度(Tg)が相対的に高い第2のアクリル系共重合体(APH)を含むエマルションである。第2のアクリル系共重合体(APH)のTgは、60〜120℃である。第2のアクリル系エマルション(AEH)は、1種または2種以上用いることができる。
第2のアクリル系共重合体(APH)は、乳化剤および粘着付与樹脂(TF)の存在下で、複数種のエチレン性不飽和単量体を含むエチレン性不飽和単量体混合物(AMH)を乳化重合して得られる。
エチレン性不飽和単量体混合物(AMH)100質量部に対する粘着付与樹脂(TF)の使用量は特に制限されず、好ましくは10〜60質量部である。
(Second acrylic emulsion (AEH))
The second acrylic emulsion (AEH) is an emulsion containing a second acrylic copolymer (APH) having a relatively high glass transition temperature (Tg). The Tg of the second acrylic copolymer (APH) is 60 to 120 ° C. The second acrylic emulsion (AEH) can be used alone or in combination of two or more.
The second acrylic copolymer (APH) is an ethylenically unsaturated monomer mixture (AMH) containing a plurality of kinds of ethylenically unsaturated monomers in the presence of an emulsifier and a tackifier resin (TF). Obtained by emulsion polymerization.
The amount of the tackifier resin (TF) used with respect to 100 parts by mass of the ethylenically unsaturated monomer mixture (AMH) is not particularly limited, and is preferably 10 to 60 parts by mass.
第2のアクリル系共重合体(APH)のTgが60〜120℃となるように、原料の複数種のエチレ
ン性不飽和単量体を選択し、重合条件を決定する。第2のアクリル系共重合体(APH)のTgが上記範囲にあることで、良好な接着力・曲面貼付性と良好な保持力との両立が可能となる。Tgは、より好ましくは80〜115℃、特に好ましくは90〜110℃である。
A plurality of types of ethylenically unsaturated monomers as raw materials are selected so that the Tg of the second acrylic copolymer (APH) is 60 to 120 ° C., and the polymerization conditions are determined. When the Tg of the second acrylic copolymer (APH) is in the above range, it is possible to achieve both good adhesive strength / curved surface stickability and good holding power. Tg is more preferably 80 to 115 ° C, particularly preferably 90 to 110 ° C.
<エチレン性不飽和単量体混合物(AMH)>
第2のアクリル系エマルション(AEH)は、エチレン性不飽和単量体混合物(AMH)の乳化重合物である。
エチレン性不飽和単量体混合物(AMH)は、直鎖または分岐鎖のアルコールと(メタ)アクリル酸とのエステルである1種以上の(メタ)アクリル酸アルキルエステルを含み、必要に応じて、1種以上の他の単量体を含むことができる。(メタ)アクリル酸アルキルエステルおよび他の単量体の例示は、エチレン性不飽和単量体混合物(AML)と同様である。
<Ethylene unsaturated monomer mixture (AMH)>
The second acrylic emulsion (AEH) is an emulsion polymer of an ethylenically unsaturated monomer mixture (AMH).
The ethylenically unsaturated monomeric mixture (AMH) comprises one or more (meth) acrylic acid alkyl esters, which are esters of linear or branched alcohols with (meth) acrylic acid, and optionally. It can contain one or more other monomers. Examples of the (meth) acrylic acid alkyl ester and other monomers are similar to the ethylenically unsaturated monomer mixture (AML).
エチレン性不飽和単量体混合物(AMH)中の(メタ)アクリル酸アルキルエステルの含有量は、好ましくは80.0〜99.5質量%、好ましくは90.0〜99.0質量%、より好ましくは97.0〜98.5質量%である。
エチレン性不飽和単量体混合物(AMH)は、メチルメタクリレート(MMA)を含むことが好ましく、メチルメタクリレート(MMA)とアクリル酸(AA)とを含むことがより好ましい。
エチレン性不飽和単量体混合物(AMH)中のメチルメタクリレート(MMA)の含有量が80質量%以上である場合、粘着付与樹脂(TF)の溶解、並びに、感圧式接着シートの曲面貼付性の向上と高温環境下における凝集力(高温保持力)の向上が容易となり、好ましい。
The content of the (meth) acrylic acid alkyl ester in the ethylenically unsaturated monomer mixture (AMH) is preferably 80.0 to 99.5% by mass, preferably 90.0 to 99.0% by mass. It is preferably 97.0 to 98.5% by mass.
The ethylenically unsaturated monomer mixture (AMH) preferably contains methyl methacrylate (MMA), more preferably methyl methacrylate (MMA) and acrylic acid (AA).
When the content of methyl methacrylate (MMA) in the ethylenically unsaturated monomer mixture (AMH) is 80% by mass or more, the tackifier resin (TF) is dissolved and the pressure-sensitive adhesive sheet has a curved surface stickability. It is preferable because it facilitates improvement and improvement of cohesive force (high temperature holding force) in a high temperature environment.
エチレン性不飽和単量体混合物(AMH)は、カルボキシ基を有するエチレン性不飽和単量体を含む場合、エチレン性不飽和単量体混合物(AMH)100質量%中のカルボキシ基を有するエチレン性不飽和単量体の含有量は、好ましくは0.5〜5.0質量%、より好ましく1.0〜3.0質量%である。使用量がこの範囲内にあることで、合成時の凝集物の発生が抑制され、中和後のハンドリングの良好なエマルションが得られやすい。 When the ethylenically unsaturated monomer mixture (AMH) contains an ethylenically unsaturated monomer having a carboxy group, it is ethylenically having a carboxy group in 100% by mass of the ethylenically unsaturated monomer mixture (AMH). The content of the unsaturated monomer is preferably 0.5 to 5.0% by mass, more preferably 1.0 to 3.0% by mass. When the amount used is within this range, the generation of agglomerates during synthesis is suppressed, and an emulsion with good handling after neutralization can be easily obtained.
<粘着付与樹脂(TF)>
粘着付与樹脂(TF)としては、エチレン性不飽和単量体混合物(AMH)中に溶解または分散するものを用いることができる。粘着付与樹脂(TF)としては、例えば、ロジン系樹脂、テルペン系樹脂、クマロンインデン樹脂、フェノール樹脂、キシレン樹脂、脂肪族系炭化水素樹脂、および芳香族系炭化水素樹脂等が挙げられる。
中でも、曲面貼付性向上の観点から、ロジン系樹脂、テルペン系樹脂、および芳香族系炭化水素樹脂が好ましく、ロジン系樹脂がより好ましく、重合ロジンエステル樹脂が特に好ましい。ロジン系樹脂としては、例えば、天然ロジン、ロジンエステル、水添ロジン、水添ロジンエステル、重合ロジン、重合ロジンエステル、不均化ロジン、および不均化ロジンエステル等が挙げられる。テルペン系樹脂としては、例えば、α−ピネン樹脂、β−ピネン樹脂、およびテルペンフェノール樹脂等が挙げられる。芳香族系炭化水素樹脂としては、例えば、スチレンおよびαメチルスチレンの共重合体等が挙げられる。粘着付与樹脂(TF)は、1種または2種以上用いることができる。
<Adhesive-imparting resin (TF)>
As the tackifier resin (TF), a resin that dissolves or disperses in an ethylenically unsaturated monomer mixture (AMH) can be used. Examples of the tackifier resin (TF) include rosin-based resin, terpene-based resin, kumaron inden resin, phenol resin, xylene resin, aliphatic hydrocarbon resin, and aromatic hydrocarbon resin.
Among them, a rosin-based resin, a terpene-based resin, and an aromatic hydrocarbon resin are preferable, a rosin-based resin is more preferable, and a polymerized rosin ester resin is particularly preferable, from the viewpoint of improving the adhesiveness to a curved surface. Examples of the rosin-based resin include natural rosin, rosin ester, hydrogenated rosin, hydrogenated rosin ester, polymerized rosin, polymerized rosin ester, disproportionated rosin, and disproportionated rosin ester. Examples of the terpene resin include α-pinene resin, β-pinene resin, terpene phenol resin and the like. Examples of the aromatic hydrocarbon resin include copolymers of styrene and α-methylstyrene. One type or two or more types of tackifier resin (TF) can be used.
接着力および曲面貼付性の観点から、粘着付与樹脂(TF)としては、軟化点が100℃以上であるものが好ましく、120℃以上であるものがより好ましく、130℃以上であるものが特に好ましく、150℃以上であるものが最も好ましい。
市販の粘着付与樹脂(TF)としては、例えば、軟化点125℃の重合ロジンエステルであるペンセルD−125(荒川化学工業社製)、軟化点160℃の重合ロジンエステルであるペンセルD−160(荒川化学工業社製)、軟化点100℃のロジンエステルであるPINEREZ2410(LAWTER社製)、軟化点115℃のテルペン樹脂であるYSレジンPX1150(ヤスハラケミカル社製)、および軟化点160℃のテルペンフェノール樹脂であるYSポリスターT160(ヤスハラケミカル社製)等が挙げられる。
粘着付与樹脂(TF)は、公知方法により合成して用いてもよい(後記[実施例]の項の製造例21〜25を参照されたい。)。
From the viewpoint of adhesive strength and curved surface stickability, the tackifier resin (TF) preferably has a softening point of 100 ° C. or higher, more preferably 120 ° C. or higher, and particularly preferably 130 ° C. or higher. , 150 ° C. or higher is most preferable.
Examples of the commercially available tackifier resin (TF) include Pencel D-125 (manufactured by Arakawa Chemical Industries, Ltd.), which is a polymerized rosin ester having a softening point of 125 ° C., and Pencel D-160 (manufactured by Arakawa Chemical Industries, Ltd.), which is a polymerized rosin ester having a softening point of 160 ° C. Arakawa Chemical Industry Co., Ltd.), PINEREZ2410 (manufactured by LAWSTER), a rosin ester with a softening point of 100 ° C., YS resin PX1150 (manufactured by Yasuhara Chemical Co., Ltd.), a terpene resin with a softening point of 115 ° C., and a terpene phenol resin with a softening point of 160 ° C. YS Polystar T160 (manufactured by Yasuhara Chemical Co., Ltd.) and the like.
The tackifier resin (TF) may be synthesized and used by a known method (see Production Examples 21 to 25 in the section [Example] below).
接着力および曲面貼付性の観点から、粘着付与樹脂(TF)としては、軟化点130℃以上のロジン系樹脂が好ましく、軟化点130℃以上の重合ロジンエステル樹脂が特に好ましい。 From the viewpoint of adhesive strength and curved surface stickability, the tackifier resin (TF) is preferably a rosin-based resin having a softening point of 130 ° C. or higher, and particularly preferably a polymerized rosin ester resin having a softening point of 130 ° C. or higher.
下記式(1)で表される温度差(Td)(第2のアクリル系共重合体(APH)のガラス転移温度(Tg)と粘着付与樹脂(TF)の軟化点との温度差の絶対値)は、好ましくは100℃以下、より好ましくは80℃以下である。この温度差が100℃以下であることで、良好な曲面貼付性・高い接着力と保持力とを効果的に両立することができる。
第2のアクリル系共重合体(APH)のTgと粘着付与樹脂(TF)の軟化点は、どちらが高くてもよい。粘着付与樹脂(TF)の軟化点が第2のアクリル系共重合体(APH)のTgよりも高いことが好ましく、その場合、良好な曲面貼付性・高い接着力と保持力とをより効果的に両立することができる。
The absolute value of the temperature difference (Td) represented by the following formula (1) (the temperature difference between the glass transition temperature (Tg) of the second acrylic copolymer (APH) and the softening point of the tackifier resin (TF)). ) Is preferably 100 ° C. or lower, more preferably 80 ° C. or lower. When this temperature difference is 100 ° C. or less, it is possible to effectively achieve both good curved surface stickability, high adhesive strength, and holding power.
Either the Tg of the second acrylic copolymer (APH) or the softening point of the tackifier resin (TF) may be higher. The softening point of the tackifier resin (TF) is preferably higher than the Tg of the second acrylic copolymer (APH), in which case good curved surface stickability, high adhesive strength and holding power are more effective. Can be compatible with.
式(1):
[温度差(Td)(℃)]=|[第2のアクリル系共重合体(APH)のTg(℃)]−[粘着付与樹脂(TF)の軟化点(℃)]|
Equation (1):
[Temperature difference (Td) (° C.)] = | [Tg (° C.) of the second acrylic copolymer (APH)]-[Softening point (° C.) of the tackifier resin (TF)] |
(第2のアクリル系エマルション(APH)の製造方法)
ガラス転移温度(Tg)が60〜120℃である第2のアクリル系共重合体(APH)を含む第2のアクリル系エマルション(APH)は、乳化剤および粘着付与樹脂(TF)の存在下で、複数種のエチレン性不飽和単量体を含むエチレン性不飽和単量体混合物(AMH)を乳化重合することで得られる(工程(2))。
粘着付与樹脂(TF)の使用量は特に制限されず、エチレン性不飽和単量体混合物(AMH)100質量部に対して、好ましくは10〜60質量部である。下限値は、より好ましくは20質量部、特に好ましくは30質量部である。上限値は、より好ましくは50質量部である。使用量がこの範囲にあることで、良好な接着力・曲面貼付性と保持力とを両立することができ、かつ、エマルション合成時の凝集物の発生を抑えることができる。
(Method for Producing Second Acrylic Emulsion (APH))
The second acrylic emulsion (APH) containing the second acrylic copolymer (APH) having a glass transition temperature (Tg) of 60 to 120 ° C. is in the presence of an emulsifier and a tackifier resin (TF). It is obtained by emulsion polymerization of an ethylenically unsaturated monomer mixture (AMH) containing a plurality of types of ethylenically unsaturated monomers (step (2)).
The amount of the tackifier resin (TF) used is not particularly limited, and is preferably 10 to 60 parts by mass with respect to 100 parts by mass of the ethylenically unsaturated monomer mixture (AMH). The lower limit is more preferably 20 parts by mass, and particularly preferably 30 parts by mass. The upper limit is more preferably 50 parts by mass. When the amount used is within this range, it is possible to achieve both good adhesive strength / curved surface stickability and holding power, and it is possible to suppress the generation of agglomerates during emulsion synthesis.
工程(2)は、
エチレン性不飽和単量体混合物(AMH)中に粘着付与樹脂(TF)を溶解させる工程(2−a)と、
得られた混合溶液を、乳化剤および水の存在下で強制乳化させて、乳化物を得る工程(2−b)と、
得られた乳化物を乳化重合する工程(2−c)とを含むことが好ましい。
Step (2) is
The step (2-a) of dissolving the tackifier resin (TF) in the ethylenically unsaturated monomer mixture (AMH), and
The step (2-b) of forcibly emulsifying the obtained mixed solution in the presence of an emulsifier and water to obtain an emulsion,
It is preferable to include a step (2-c) of emulsion polymerization of the obtained emulsion.
工程(2−a)〜(2−c)を含む工程(2)は、重合時の凝集物の発生を抑える点、および、重合時に粘着付与樹脂(TF)を溶解させるための有機溶剤を使用しなくてよい点で、好ましい。
カルボキシ基を有する単量体を使用する場合、工程(2)はさらに必要に応じて、工程(2−c)で得られた共重合体に含まれるカルボキシ基の一部または全部を、アンモニア、有機アミン、水酸化カリウム、クエン酸ナトリウム、および水酸化ナトリウム等の塩基性化合物を用いて中和する工程(2−d)を含むことができる。
The step (2) including the steps (2-a) to (2-c) uses an organic solvent for suppressing the generation of agglomerates during polymerization and for dissolving the tackifier resin (TF) during polymerization. It is preferable in that it does not have to be done.
When a monomer having a carboxy group is used, in step (2), if necessary, a part or all of the carboxy group contained in the copolymer obtained in step (2-c) is added to ammonia. The step (2-d) of neutralizing with a basic compound such as an organic amine, potassium hydroxide, sodium citrate, and sodium hydroxide can be included.
乳化重合に用いて好適な乳化剤、重合開始剤、および連鎖移動剤の例示は、第1のアクリル系エマルション(AEL)と同様である。 Examples of emulsifiers, polymerization initiators, and chain transfer agents suitable for use in emulsion polymerization are similar to those of the first acrylic emulsion (AEL).
工程(2−b)で得られる乳化物は、複数のエチレン性不飽和単量体と粘着付与樹脂(TF)と界面活性剤と水とを含む。この乳化物に含まれる油溶成分の平均粒子径は特に制限されず、エマルション合成時の凝集物の生成の抑制、および、エマルションの放置安定性の観点から、好ましくは0.3〜2.0μm、より好ましくは0.4〜1.5μm、特に好ましくは0.5〜1.2μmである。油溶成分の平均粒子径が0.3μm未満の場合は、乳化物の粘度が高くなりすぎ、強制乳化に必要なエネルギーおよび時間が多くなり生産性が低下する恐れがある。油溶成分の平均粒子径が2.0μmを超える場合は、エマルション合成時に凝集物の発生を招く恐れがある。
本明細書において、特に断りのない限り「乳化物の油溶成分の平均粒子径」は、水中での油滴径を動的光散乱法で測定した場合の累積体積平均径であり、例えば、日機装社製マイクロトラックUPA粒度分布計で測定された平均粒径値(メディアン径 D50)である。
The emulsion obtained in step (2-b) contains a plurality of ethylenically unsaturated monomers, a tackifier resin (TF), a surfactant, and water. The average particle size of the oil-soluble component contained in this emulsion is not particularly limited, and is preferably 0.3 to 2.0 μm from the viewpoint of suppressing the formation of agglomerates during emulsion synthesis and the stability of the emulsion on standing. , More preferably 0.4 to 1.5 μm, and particularly preferably 0.5 to 1.2 μm. If the average particle size of the oil-soluble component is less than 0.3 μm, the viscosity of the emulsion becomes too high, and the energy and time required for forced emulsification increase, which may reduce productivity. If the average particle size of the oil-soluble component exceeds 2.0 μm, agglomerates may be generated during emulsion synthesis.
In the present specification, unless otherwise specified, the "average particle size of the oil-soluble component of the emulsion" is the cumulative volume average diameter when the oil droplet diameter in water is measured by a dynamic light scattering method, for example. It is an average particle size value (median diameter D50) measured by the Microtrac UPA particle size distribution meter manufactured by Nikkiso Co., Ltd.
強制乳化に用いる乳化機としては、回転型連続乳化機、コロイドミル型乳化機、高圧ホモジナイザー型乳化機、および超音波処理型乳化機等の公知の乳化機が使用できる。中でも、回転型連続乳化機の1種である回転子/固定子型高速回転連続型乳化機が、油溶成分の平均粒子径が好適な乳化物を得やすく、メンテナンスが容易で、単位時間あたりの処理量が多いことから、好ましい。 As the emulsifying machine used for forced emulsification, known emulsifying machines such as a rotary continuous emulsifying machine, a colloid mill type emulsifying machine, a high pressure homogenizer type emulsifying machine, and an ultrasonic treatment type emulsifying machine can be used. Among them, the rotor / stator type high-speed rotary continuous emulsifier, which is one of the rotary continuous emulsifiers, makes it easy to obtain an emulsion having a suitable average particle size of oil-soluble components, is easy to maintain, and per unit time. It is preferable because the amount of processing is large.
工程(2−c)で行う乳化重合の手法としては、第1のアクリル系エマルション(AEL)の乳化重合と同様の手法を用いることができる。工程(2−b)において、単量体混合物と粘着付与樹脂(TF)との乳化物に含まれる油溶成分の平均粒子径(メディアン径)を調整することで、より水性接着剤の性能に優れたエマルションが得られる。 As the emulsion polymerization method performed in the step (2-c), the same method as the emulsion polymerization of the first acrylic emulsion (AEL) can be used. In step (2-b), by adjusting the average particle size (median size) of the oil-soluble component contained in the emulsion of the monomer mixture and the tackifier resin (TF), the performance of the water-based adhesive can be improved. An excellent emulsion can be obtained.
第2のアクリル系エマルション(AEH)の製造に使用される乳化剤の使用量(ここで言う使用量は、有効成分量である。)は、エチレン性不飽和単量体混合物(AMH)と粘着付与樹脂(TF)との合計100質量部に対して、好ましくは1.0〜4.0質量部、より好ましくは1.5〜3.5質量部である。乳化剤の使用量が1.0質量部以上であることにより、エマルション製造時の凝集物の発生を抑制することができ、4.0質量部以下であることにより、感圧式接着シートの曲面貼付性がより良化する。 The amount of the emulsifier used in the production of the second acrylic emulsion (AEH) (the amount used here is the amount of the active ingredient) is tack-imparted with the ethylenically unsaturated monomer mixture (AMH). It is preferably 1.0 to 4.0 parts by mass, and more preferably 1.5 to 3.5 parts by mass with respect to 100 parts by mass of the total of the resin (TF). When the amount of the emulsifier used is 1.0 part by mass or more, the generation of agglomerates during emulsion production can be suppressed, and when it is 4.0 parts by mass or less, the curved surface stickability of the pressure-sensitive adhesive sheet can be applied. Is better.
(水性感圧式接着剤の製造方法)
水性感圧式接着剤の製造方法は、
上記工程(1)と、
上記工程(2)と、
工程(1)で得られた第1のアクリル系エマルション(AEL)と、工程(2)で得られた第2のアクリル系エマルション(AEH)とを混合する工程(3)とを有する。
第1のアクリル系エマルション(AEL)と第2のアクリル系エマルション(AEH)との混合前、混合時、または混合後に、各種添加剤を添加してもよい。添加剤としては、レベリング剤、消泡剤、粘度調整剤、防腐剤、粘着力調整のための粘着付与剤、可塑剤、充填剤、着色剤、およびシランカップリング剤等が挙げられる。
後添加の粘着付与剤としては、例えば、ロジン系樹脂、フェノール樹脂、ポリテルペン、アセチレン樹脂、石油系炭化水素樹脂、エチレン酢酸ビニル共重合体、合成ゴム、および天然ゴム等が挙げられる。
(Manufacturing method of water-based pressure-sensitive adhesive)
The manufacturing method of the water-based pressure-sensitive adhesive is
The above step (1) and
The above step (2) and
It has a step (3) of mixing the first acrylic emulsion (AEL) obtained in the step (1) and the second acrylic emulsion (AEH) obtained in the step (2).
Various additives may be added before, during, or after mixing the first acrylic emulsion (AEL) and the second acrylic emulsion (AEH). Examples of additives include leveling agents, defoaming agents, viscosity modifiers, preservatives, tackifiers for adjusting adhesive strength, plasticizers, fillers, colorants, silane coupling agents and the like.
Examples of the post-added tackifier include rosin-based resin, phenol resin, polyterpene, acetylene resin, petroleum-based hydrocarbon resin, ethylene-vinyl acetate copolymer, synthetic rubber, and natural rubber.
共重合体の分散粒子間で架橋させるため、任意の架橋剤を配合してもよい。
例えば、第1のアクリル系エマルション(AEL)または第2のアクリル系エマルション(AEH)の原料単量体として水酸基を有する単量体を用いた場合、架橋剤として、イソシアネート化合物;チタンおよびジルコニウム等のアルコキシド化合物等を用いることができる。
第1のアクリル系エマルション(AEL)または第2のアクリル系エマルション(AEH)の原料単量体としてカルボニル基を有する単量体を用いた場合、架橋剤として、アミン類およびヒドラジド化合物等を用いることができる。
第1のアクリル系エマルション(AEL)または第2のアクリル系エマルション(AEH)の原料単量体としてカルボキシ基を有する単量体を用いた場合、架橋剤として、カルボジイミド化合物;エポキシ化合物;アジリジン化合物;酸化亜鉛等の金属化合物を用いることができる。
Any cross-linking agent may be blended in order to cross-link between the dispersed particles of the copolymer.
For example, when a monomer having a hydroxyl group is used as the raw material monomer of the first acrylic emulsion (AEL) or the second acrylic emulsion (AEH), the cross-linking agent is an isocyanate compound; titanium, zirconium, or the like. An alkoxide compound or the like can be used.
When a monomer having a carbonyl group is used as the raw material monomer of the first acrylic emulsion (AEL) or the second acrylic emulsion (AEH), amines, hydrazide compounds and the like should be used as the cross-linking agent. Can be done.
When a monomer having a carboxy group is used as the raw material monomer of the first acrylic emulsion (AEL) or the second acrylic emulsion (AEH), the carbodiimide compound; epoxy compound; aziridine compound; A metal compound such as zinc oxide can be used.
[感圧式接着シート]
本発明の感圧式接着シートは、上記の本発明の水性感圧式接着剤の乾燥物からなる感圧式接着層を有する。感圧式接着層は、本発明の水性感圧式接着剤を、基材または剥離ライナー上に塗工し、乾燥させることにより、形成することができる。
[Pressure-sensitive adhesive sheet]
The pressure-sensitive adhesive sheet of the present invention has a pressure-sensitive adhesive layer made of a dried product of the above-mentioned water-based pressure-sensitive adhesive of the present invention. The pressure-sensitive adhesive layer can be formed by applying the water-based pressure-sensitive adhesive of the present invention onto a base material or a release liner and drying it.
基材としては、例えば、ポリエチレン、ポリプロピレン、およびエチレン−プロピレン共重合体等のポリオレフィン系樹脂、ポリエチレンテレフタレート等のポリエステル系樹脂、酢酸ビニル系樹脂、ポリイミド系樹脂、フッ素系樹脂、ポリ塩化ビニル系樹脂、およびセロハン等の樹脂材料からなる樹脂フィルム;天然ゴムおよびブチルゴム等からなるゴムシート;ポリウレタン、ポリクロロプレンゴム、およびポリエチレン等を発泡させた発泡体シート;クラフト紙、クレープ紙、および和紙等の紙;綿布およびスフ布等の布;セルロース系不織布、ポリエステル不織布、およびビニロン不織布等の不織布;アルミニウム箔および銅箔等の金属箔;これらの複合材等が挙げられる。
このようなシート状の基材の片面または両面には、下塗剤の塗布およびコロナ放電処理等の表面処理が施されていてもよい。基材の厚みは用途等に応じて適宜選択でき、一般的には10〜500μm、典型的には10〜200μmである。
Examples of the base material include polyolefin resins such as polyethylene, polypropylene, and ethylene-propylene copolymers, polyester resins such as polyethylene terephthalate, vinyl acetate resins, polyimide resins, fluororesins, and polyvinyl chloride resins. , And a resin film made of a resin material such as cellophane; a rubber sheet made of natural rubber and butyl rubber; a foam sheet made by foaming polyurethane, polychloroprene rubber, polyethylene, etc .; paper such as kraft paper, crepe paper, and Japanese paper. Cloths such as cotton cloth and sufu cloth; non-woven fabrics such as cellulose-based non-woven fabrics, polyester non-woven fabrics, and vinylon non-woven fabrics; metal foils such as aluminum foil and copper foil; composite materials thereof and the like.
One side or both sides of such a sheet-shaped base material may be subjected to surface treatment such as application of a primer and corona discharge treatment. The thickness of the base material can be appropriately selected depending on the intended use and the like, and is generally 10 to 500 μm, typically 10 to 200 μm.
剥離ライナー(剥離性シートまたはセパレータとも言う。)としては、公知のものを用いることができ、基材の少なくとも一方の面を、フッ素樹脂およびシリコーン樹脂等の剥離剤で処理したものが好ましい。基材としては、例えば、グラシン紙、クラフト紙、およびクレーコート紙等の紙に対して、ポリエチレン等の樹脂フィルムをラミネート、またはポリビニルアルコールおよびアクリル系ポリマー等の樹脂をコートした紙/樹脂複合材が好ましい。 As the release liner (also referred to as a release sheet or separator), a known one can be used, and one in which at least one surface of the base material is treated with a release agent such as a fluororesin or a silicone resin is preferable. As the base material, for example, a paper / resin composite material obtained by laminating a resin film such as polyethylene on paper such as glassin paper, kraft paper, and clay-coated paper, or coating a resin such as polyvinyl alcohol and acrylic polymer. Is preferable.
塗工装置としては、コンマコーター、リバースコーター、スロットダイコーター、リップコーター、グラビアチャンバーコーター、およびカーテンコーター等の各種公知のコーティング装置を用いることができる。
乾燥温度は特に制限されず、好ましくは80〜120℃である。乾燥温度が80℃未満では、乾燥が遅く、乾燥に長時間を要する。120℃よりも高温で乾燥すると、基材または剥離ライナーの熱劣化が生じる恐れがあり、好ましくない。
As the coating device, various known coating devices such as a comma coater, a reverse coater, a slot die coater, a lip coater, a gravure chamber coater, and a curtain coater can be used.
The drying temperature is not particularly limited, and is preferably 80 to 120 ° C. If the drying temperature is less than 80 ° C., the drying is slow and it takes a long time to dry. Drying at a temperature higher than 120 ° C. may cause thermal deterioration of the base material or the release liner, which is not preferable.
以上説明したように、本発明によれば、各種被着体に対する高い接着力と、良好な曲面貼付性と、高温環境下における高い凝集力(高温保持力)と、低温環境下における高い接着力とを有する水性感圧式接着剤とその製造方法、およびこれを用いた感圧式接着シートを提供することができる。
本発明の水性感圧式接着剤を用いて形成された感圧式接着層を含む感圧式接着シートは、被着体に貼付後、高温環境下でも、被着体と感圧式接着シートとの間の位置ズレ等の接着不良を抑制することができる。この感圧式接着シートは、曲面形状を有する被着体、および、一般的に接着が難しいポリオレフィン系樹脂等の低極性被着体に対しても、良好な接着力を有することができる。この感圧式接着シートは、低温環境下でも、一般的に接着が難しいポリオレフィン系樹脂等の低極性被着体に対しても、良好な接着力を有することができる。
As described above, according to the present invention, high adhesive force to various adherends, good curved surface adhesiveness, high cohesive force (high temperature holding force) in a high temperature environment, and high adhesive force in a low temperature environment. It is possible to provide an aqueous pressure-sensitive adhesive having the above, a method for producing the same, and a pressure-sensitive adhesive sheet using the same.
The pressure-sensitive adhesive sheet containing the pressure-sensitive adhesive layer formed by using the water-based pressure-sensitive adhesive of the present invention can be placed between the adherend and the pressure-sensitive adhesive sheet even in a high temperature environment after being attached to the adherend. Poor adhesion such as misalignment can be suppressed. This pressure-sensitive adhesive sheet can have good adhesive force even for an adherend having a curved surface shape and a low-polarity adherend such as a polyolefin resin which is generally difficult to adhere. This pressure-sensitive adhesive sheet can have good adhesive force even in a low temperature environment even for a low-polarity adherend such as a polyolefin resin, which is generally difficult to adhere.
本発明に係る実施例、および比較例について説明する。特に断りのない限り、「部」は「質量部」を、「%」は「質量%」をそれぞれ示す。水および溶剤以外の成分の配合量は、不揮発分換算値である。「RH」は、相対湿度を示す。 Examples and comparative examples according to the present invention will be described. Unless otherwise specified, "parts" indicates "parts by mass" and "%" indicates "% by mass". The blending amounts of components other than water and solvent are non-volatile content conversion values. "RH" indicates relative humidity.
乳化物の油溶成分の平均粒子径の測定方法、アクリル系共重合体のガラス転移温度(Tg)の計算方法、粘着付与樹脂(TF)の重量平均分子量(Mw)の測定方法、および粘着付与樹脂(TF)の軟化点の測定方法は、以下の通りである。 A method for measuring the average particle size of the oil-soluble component of the emulsion, a method for calculating the glass transition temperature (Tg) of the acrylic copolymer, a method for measuring the weight average molecular weight (Mw) of the tackifier resin (TF), and a method for tackling. The method for measuring the softening point of the resin (TF) is as follows.
[乳化物の油溶成分の平均粒子径]
乳化物の油溶成分の平均粒子径として、水中での油滴径を動的光散乱法で測定した場合の累積体積平均径を測定した。日機装社製マイクロトラックUPA粒度分布計を用いて、平均粒径値(メディアン径 D50)を求めた。
[Average particle size of oil-soluble components of emulsion]
As the average particle diameter of the oil-soluble component of the emulsion, the cumulative volume average diameter when the oil droplet diameter in water was measured by the dynamic light scattering method was measured. The average particle size value (median diameter D50) was determined using a Microtrack UPA particle size distribution meter manufactured by Nikkiso Co., Ltd.
[アクリル系共重合体のガラス転移温度(Tg)]
アクリル系共重合体のTgは、各原料単量体の単独重合体のTgを基に、FOXの式により理論的に算出した。計算に用いた各種単独重合体のTgを下記に示す。
2−エチルヘキシルアクリレート(2−EHA)の単独重合体:−70℃、
ブチルアクリレート(BA)の単独重合体:−54℃、
メチルメタクリレート(MMA)の単独重合体:105℃、
アクリル酸(AA)の単独重合体:106℃、
メタクリル酸(MAA)の単独共重合体:130℃。
[Glass transition temperature (Tg) of acrylic copolymer]
The Tg of the acrylic copolymer was theoretically calculated by the FOX formula based on the Tg of the homopolymer of each raw material monomer. The Tg of various homopolymers used in the calculation is shown below.
Copolymer of 2-ethylhexyl acrylate (2-EHA): -70 ° C,
Butyl acrylate (BA) homopolymer: -54 ° C,
Homopolymer of methyl methacrylate (MMA): 105 ° C,
Acrylic acid (AA) homopolymer: 106 ° C,
Methacrylic acid (MAA) homopolymer: 130 ° C.
[粘着付与樹脂(TF)の重量平均分子量(Mw)]
粘着付与樹脂(TF)のMwは、GPC(ゲルパーミエーションクロマトグラフィ)を用いて測定した。GPCは、溶媒に溶解した物質をその分子サイズの差によって分離定量する液体クロマトグラフィである。標準ポリスチレンを用いた換算により、Mwを決定した。測定条件は、以下の通りである。
装置名:島津製作所製、LC−GPCシステム「Prominence」、
カラム:東ソー(株)製「GMHXL」を4本と東ソー(株)製「HXL−H」を1本とを直列に繋いだもの、
溶媒:テトラヒドロフラン(THF)、
流量:1.0ml/min、
カラム温度:40℃。
[Weight average molecular weight (Mw) of adhesive-imparting resin (TF)]
The Mw of the tackifier resin (TF) was measured using GPC (gel permeation chromatography). GPC is a liquid chromatography in which a substance dissolved in a solvent is separated and quantified by the difference in its molecular size. Mw was determined by conversion using standard polystyrene. The measurement conditions are as follows.
Device name: Shimadzu, LC-GPC system "Prominence",
Column: Four "GMHXL" manufactured by Tosoh Co., Ltd. and one "HXL-H" manufactured by Tosoh Co., Ltd. are connected in series.
Solvent: tetrahydrofuran (THF),
Flow rate: 1.0 ml / min,
Column temperature: 40 ° C.
[粘着付与樹脂(TF)の軟化点]
粘着付与樹脂(TF)の軟化点は、JIS K 2425に準拠して、環球法により測定した。
[Softening point of adhesive resin (TF)]
The softening point of the tackifier resin (TF) was measured by the ring-and-ball method in accordance with JIS K 2425.
[製造例11](第1のアクリル系エマルション(AEL−1)の製造)
2−エチルヘキシルアクリレート(2−EHA)32.0部と、ブチルアクリレート(BA)64.0部と、メチルメタクリレート(MMA)3.1部と、アクリル酸(AA)0.9部と、連鎖移動剤としてチオグリコール酸オクチル0.09部と、アニオン性乳化剤としてアクアロンKH−10(第一工業製薬製)1.2部をイオン交換水4.8部に溶解させたものと、イオン交換水13.5部とを撹拌混合し、乳化物を得た。これを滴下ロートに入れた。
撹拌機、冷却管、温度計、および上記滴下ロートを取り付けた4つ口フラスコに、イオン交換水31.5部を仕込み、フラスコ内部の空気を窒素ガスで置換し、撹拌しながら内温を82℃まで昇温し、3%過硫酸カリウム水溶液を2.1部添加した。10分後、上記滴下ロートから上記乳化物の滴下を開始し、これと並行して3%過硫酸カリウム水溶液6.3部を別の滴下ロートから5時間かけて滴下した。
内温を76℃に保ったまま、さらに撹拌しながら2時間熟成した後に冷却し、アンモニア水を用いて中和し、固形分62%の第1のアクリル系共重合体(APL−1)のエマルション(第1のアクリル系エマルション(AEL−1))を得た。第1のアクリル系共重合体(APL−1)のTgは−51.5℃であった。第1のアクリル系共重合体(APL−1)の単量体組成とTgを表1に示す。
[Production Example 11] (Production of First Acrylic Emulsion (AEL-1))
Chain transfer with 32.0 parts of 2-ethylhexyl acrylate (2-EHA), 64.0 parts of butyl acrylate (BA), 3.1 parts of methyl methacrylate (MMA), and 0.9 parts of acrylic acid (AA). 0.09 part of octyl thioglycolate as an agent, 1.2 parts of Aqualon KH-10 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) as an anionic emulsifier dissolved in 4.8 parts of ion-exchanged water, and ion-exchanged water 13 .5 parts were stirred and mixed to obtain an emulsion. This was placed in a dropping funnel.
31.5 parts of ion-exchanged water was charged into a four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and the above-mentioned dropping funnel, the air inside the flask was replaced with nitrogen gas, and the internal temperature was adjusted to 82 while stirring. The temperature was raised to ° C., and 2.1 parts of a 3% potassium persulfate aqueous solution was added. After 10 minutes, the emulsion was started to be dropped from the dropping funnel, and in parallel with this, 6.3 parts of a 3% potassium persulfate aqueous solution was dropped from another dropping funnel over 5 hours.
While maintaining the internal temperature at 76 ° C., the mixture was aged for 2 hours with further stirring, cooled, neutralized with aqueous ammonia, and the first acrylic copolymer (APL-1) having a solid content of 62%. An emulsion (first acrylic emulsion (AEL-1)) was obtained. The Tg of the first acrylic copolymer (APL-1) was −51.5 ° C. Table 1 shows the monomer composition and Tg of the first acrylic copolymer (APL-1).
[製造例12、13](第1のアクリル系エマルション(AEL−2)、(AEL−3)の製造)
単量体組成を変更した以外は、製造例11と同様の方法にて、固形分62%の第1のアクリル系共重合体(APL)のエマルション(第1のアクリル系エマルション(AEL))を得た。第1のアクリル系共重合体(APL)の主な原料組成とTgを表1に示す。表1の各製造例において、表に不記載の条件は共通条件とした。
[Production Examples 12 and 13] (Production of First Acrylic Emulsion (AEL-2), (AEL-3))
An emulsion of the first acrylic copolymer (APL) having a solid content of 62% (first acrylic emulsion (AEL)) was prepared in the same manner as in Production Example 11 except that the monomer composition was changed. Obtained. Table 1 shows the main raw material compositions and Tg of the first acrylic copolymer (APL). In each production example in Table 1, the conditions not shown in the table were set as common conditions.
[製造例21](粘着付与樹脂(TF−1)の製造)
(粘着付与樹脂(TF−1)の製造)
<重合反応工程>
温度計、攪拌機、窒素導入管、および減圧装置を備えた反応装置に、ガムロジン1000部、キシレン1000部、および重合触媒として塩化亜鉛50部を仕込み、140℃で7時間、重合反応を行った。反応生成物のキシレン溶液を温水で洗浄した後、濃塩酸10部および温水700部を加えて洗浄した。さらに500部の温水を用いた洗浄を2回実施した後、液温200℃未満、減圧度1300Paの条件下でキシレンを留去した。さらに液温200〜275℃、減圧度400Paの条件下でガムロジンの分解物および未反応ロジンを留去して、重合ロジン(R−1)を得た。
[Manufacturing Example 21] (Manufacturing of Adhesive-Applying Resin (TF-1))
(Manufacturing of adhesive resin (TF-1))
<Polymerization reaction process>
1000 parts of gumrosin, 1000 parts of xylene, and 50 parts of zinc chloride as a polymerization catalyst were charged into a reactor equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a decompression device, and a polymerization reaction was carried out at 140 ° C. for 7 hours. The xylene solution of the reaction product was washed with warm water, and then 10 parts of concentrated hydrochloric acid and 700 parts of warm water were added for washing. Further, after washing with 500 parts of warm water twice, xylene was distilled off under the conditions of a liquid temperature of less than 200 ° C. and a reduced pressure of 1300 Pa. Further, a decomposition product of gum rosin and an unreacted rosin were distilled off under the conditions of a liquid temperature of 200 to 275 ° C. and a reduced pressure of 400 Pa to obtain a polymerized rosin (R-1).
<エステル化反応工程>
温度計、攪拌機、窒素導入管、および減圧装置を備えた反応装置に、重合ロジン(R−1)500部およびペンタエリスリトール60部を仕込み、窒素気流下にて250℃で2時間反応させ、さらに270℃で10時間、エステル化反応を行い、粘着付与樹脂(TF−1)(重合ロジンエステル)を得た。得られた粘着付与樹脂は、軟化点が158℃、Mwが3200であった。エステル化反応の原料組成と、粘着付与樹脂(TF)の軟化点およびMwを表2に示す。
<Esterification reaction process>
A reaction device equipped with a thermometer, a stirrer, a nitrogen introduction tube, and a decompression device was charged with 500 parts of polymerized rosin (R-1) and 60 parts of pentaerythritol, reacted at 250 ° C. for 2 hours under a nitrogen stream, and further. The esterification reaction was carried out at 270 ° C. for 10 hours to obtain a tackifier resin (TF-1) (polymerized rosin ester). The obtained tackifier resin had a softening point of 158 ° C. and an Mw of 3200. Table 2 shows the raw material composition of the esterification reaction, the softening point of the tackifier resin (TF), and Mw.
[製造例22〜25](粘着付与樹脂(TF−2)〜(TF−5)の製造)
エステル化反応工程の原料組成を変更した以外は、製造例21と同様の方法にて、粘着付与樹脂(TF−2)〜(TF−5)(いずれも重合ロジンエステル)を得た。エステル化反応の原料組成と、粘着付与樹脂(TF)の軟化点およびMwを表2に示す。表2の各製造例において、表に不記載の条件は共通条件とした。
[Production Examples 22 to 25] (Production of Adhesive Resins (TF-2) to (TF-5))
Adhesive-imparting resins (TF-2) to (TF-5) (both polymerized rosin esters) were obtained in the same manner as in Production Example 21 except that the raw material composition in the esterification reaction step was changed. Table 2 shows the raw material composition of the esterification reaction, the softening point of the tackifier resin (TF), and Mw. In each production example in Table 2, the conditions not shown in the table were set as common conditions.
[市販の粘着付与樹脂(TF)]
用意した市販の粘着付与樹脂(TF)は、以下の通りである。
(TF−6)ヤスハラケミカル製「YSポリスターT−160」、テルペン系樹脂(テルペンフェノール樹脂)、軟化点160℃、
(TF−7)三井化学製「FTR−6100」、芳香族系炭化水素樹脂(スチレン系・脂肪族モノマー共重合体)、軟化点95℃。
用意した市販の粘着付与樹脂(TF)のリストを表3に示しておく。
[Commercially available adhesive resin (TF)]
The prepared commercially available tackifier resin (TF) is as follows.
(TF-6) Yasuhara Chemical "YS Polystar T-160", terpene resin (terpene phenol resin), softening point 160 ° C,
(TF-7) "FTR-6100" manufactured by Mitsui Chemicals, aromatic hydrocarbon resin (styrene-based / aliphatic monomer copolymer), softening point 95 ° C.
Table 3 shows a list of prepared commercially available tackifying resins (TFs).
[製造例31](第2のアクリル系エマルション(AEH−1)の製造)
メチルメタクリレート(MMA)98部およびアクリル酸(AA)2部の混合物に、粘着付与樹脂(TF−1)を40部溶解させた。これに、アニオン系乳化剤としてニューコール707SF(ポリオキシエチレン多環フェニルエーテル硫酸エステル塩の水溶液、有効成分30%、日本乳化剤社製)14.0部、およびイオン交換水29.7部を加え、撹拌混合して、乳化物を得た。さらに、回転子/固定子としてスリット式ユニットを使用したキャビトロンCD1010型(株式会社ユーロテック製)を用いて、強制乳化させて、油溶成分の平均粒子径(メディアン径)が0.6μmの乳化物を得た。これを滴下ロートに入れた。
[Production Example 31] (Production of a second acrylic emulsion (AEH-1))
40 parts of the tackifier resin (TF-1) was dissolved in a mixture of 98 parts of methyl methacrylate (MMA) and 2 parts of acrylic acid (AA). To this, 14.0 parts of Newcol 707SF (aqueous solution of polyoxyethylene polycyclic phenyl ether sulfate ester salt, active ingredient 30%, manufactured by Nippon Emulsifier Co., Ltd.) and 29.7 parts of ion-exchanged water were added as anionic emulsifiers. The mixture was stirred and mixed to obtain an emulsion. Further, a Cavitron CD1010 type (manufactured by Eurotech Co., Ltd.) using a slit type unit as a rotor / stator is used for forced emulsification to emulsify an oil-soluble component having an average particle diameter (median diameter) of 0.6 μm. I got something. This was placed in a dropping funnel.
撹拌機、冷却管、温度計、および上記滴下ロートを取り付けた4つ口フラスコに、脱イオン水22.4部を仕込み、フラスコ内部を窒素ガスで置換し、撹拌しながら内温を80℃まで昇温し、7.4%過硫酸アンモニウム水溶液を1.1部添加した。5分後、上記滴下ロートから上記乳化物の滴下を開始し、これと並行して7.4%過硫酸アンモニウム水溶液2.7部を別の滴下ロートから3時間かけて滴下した。内温を80℃に保ったまま、さらに撹拌しながら76℃にて4時間熟成した後に冷却し、アンモニア水を用いて中和して、固形分60%の第2のアクリル系共重合体(APH−1)のエマルション(第2のアクリル系エマルション(AEH−1))を得た。第2のアクリル系共重合体(APH−1)のTgは105℃であった。第2のアクリル系共重合体(APH−1)の主な原料組成とTgを表4−1に示す。 22.4 parts of deionized water was placed in a four-necked flask equipped with a stirrer, a cooling tube, a thermometer, and the above-mentioned dropping funnel, the inside of the flask was replaced with nitrogen gas, and the internal temperature was raised to 80 ° C. while stirring. The temperature was raised, and 1.1 parts of a 7.4% ammonium persulfate aqueous solution was added. After 5 minutes, the emulsion was started to be dropped from the dropping funnel, and in parallel with this, 2.7 parts of a 7.4% ammonium persulfate aqueous solution was dropped from another dropping funnel over 3 hours. While maintaining the internal temperature at 80 ° C., the mixture was aged at 76 ° C. for 4 hours with further stirring, cooled, and neutralized with aqueous ammonia to obtain a second acrylic copolymer having a solid content of 60%. An emulsion of APH-1) (second acrylic emulsion (AEH-1)) was obtained. The Tg of the second acrylic copolymer (APH-1) was 105 ° C. The main raw material compositions and Tg of the second acrylic copolymer (APH-1) are shown in Table 4-1.
[製造例32〜41](第2のアクリル系エマルション(AEH−2)〜(AEH−11)の製造)
原料組成を変更した以外は、製造例31と同様の方法にて、固形分60%の第2のアクリル系共重合体(APH)のエマルション(第2のアクリル系エマルション(AEH))を得た。第2のアクリル系共重合体(APH)の主な原料組成とTgを表4−1、表4−2に示す。表4−1および表4−2の各製造例において、表に不記載の条件は共通条件とした。
[Production Examples 32 to 41] (Production of Second Acrylic Emulsions (AEH-2) to (AEH-11))
An emulsion of a second acrylic copolymer (APH) having a solid content of 60% (second acrylic emulsion (AEH)) was obtained by the same method as in Production Example 31 except that the raw material composition was changed. .. The main raw material compositions and Tg of the second acrylic copolymer (APH) are shown in Tables 4-1 and 4-2. In each production example of Table 4-1 and Table 4-2, the conditions not shown in the table were set as common conditions.
(実施例1)
<水性感圧式接着剤の作製>
第1のアクリル系共重合体(APL−1)と第2のアクリル系共重合体(APH−1)との質量比が90.6:9.4になるように、第1のアクリル系エマルション(AEL−1)と第2のアクリル系エマルション(AEH−1)とを撹拌混合した。この混合物に対してアンモニア水を添加して、pHを8.5に調整した。これに、消泡剤、レベリング剤、および防腐剤を加え、さらに粘度調整剤を添加して、粘度を4000mPa・s(BL型粘度計、#4ローター使用、60rpmの条件で測定)に調整し、水性感圧式接着剤を得た。
(Example 1)
<Manufacturing of water-based pressure-sensitive adhesive>
The first acrylic emulsion so that the mass ratio of the first acrylic copolymer (APL-1) to the second acrylic copolymer (APH-1) is 90.6: 9.4. (AEL-1) and the second acrylic emulsion (AEH-1) were stirred and mixed. Ammonia water was added to this mixture to adjust the pH to 8.5. A defoaming agent, a leveling agent, and a preservative are added to this, and a viscosity adjusting agent is further added to adjust the viscosity to 4000 mPa · s (BL type viscometer, using # 4 rotor, measured under the condition of 60 rpm). , A water-based pressure-sensitive adhesive was obtained.
<感圧式接着シートの作製>
コンマコーターを用いて、得られた水性感圧式接着剤を剥離紙上に、乾燥後の膜の質量が16g/m2となるように塗工し、105℃の乾燥オーブンを用いて60秒間乾燥し、この上に上質紙(60g/m2)を貼り合わせ、得られた感圧式接着シートを巻き取った。幅25mm、長さ100mmの感圧式接着シートを準備し、後記評価に供した。感圧式接着シートの長さ方向は、製造時のシートの流れ方向に合わせた。
水性感圧式接着剤の主な配合組成と感圧式接着シートの評価結果を表5−1に示す。表5−1、表5−2、表6−1、および表6−2において、非記載の条件は共通条件とした。
<Making a pressure-sensitive adhesive sheet>
Using a comma coater, the obtained water-based pressure-sensitive adhesive was applied onto a release paper so that the mass of the film after drying was 16 g / m 2, and dried in a drying oven at 105 ° C. for 60 seconds. , High-quality paper (60 g / m 2 ) was laminated on this, and the obtained pressure-sensitive adhesive sheet was wound up. A pressure-sensitive adhesive sheet having a width of 25 mm and a length of 100 mm was prepared and used for the evaluation described later. The length direction of the pressure-sensitive adhesive sheet was adjusted to the flow direction of the sheet at the time of manufacture.
Table 5-1 shows the main composition of the water-based pressure-sensitive adhesive and the evaluation results of the pressure-sensitive adhesive sheet. In Table 5-1 and Table 5-2, Table 6-1 and Table 6-2, the conditions not described are common conditions.
(実施例2〜12、比較例1、比較例5〜8)
実施例2〜12、比較例1、および比較例5〜8の各例では、表5−1、表5−2、表6−1、および表6−2に示すように、第1のアクリル系エマルション(APL)と第2のアクリル系エマルション(APH)の種類と配合比を変更した以外は、実施例1と同様にして、水性感圧式接着剤および感圧式接着シートを作製し、評価した。主な配合組成と評価結果を表5−1、表5−2、表6−1、および表6−2に示す。
(Examples 2 to 12, Comparative Example 1, Comparative Examples 5 to 8)
In each of Examples 2 to 12, Comparative Example 1 and Comparative Examples 5 to 8, the first acrylic as shown in Table 5-1, Table 5-2, Table 6-1 and Table 6-2. A water-based pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were prepared and evaluated in the same manner as in Example 1 except that the types and compounding ratios of the system emulsion (APL) and the second acrylic emulsion (APH) were changed. .. The main composition and evaluation results are shown in Tables 5-1 and 5-2, Table 6-1 and Table 6-2.
(比較例2〜4)
比較例2では、第1のアクリル系エマルション(AEL−1)と第2のアクリル系エマルション(AEH−1)の代わりに、第1のアクリル系エマルション(AEL−1)と市販の下記の粘着付与樹脂の水分散体とを表6−1に示す配合比で用いた以外は、実施例1と同様にして、水性感圧式接着剤および感圧式接着シートを作製し、評価した。
比較例3、4では、第1のアクリル系エマルション(AEL−1)と第2のアクリル系エマルション(AEH−1)の代わりに、第1のアクリル系エマルション(AEL−1)と粘着付与樹脂(TF)を含まない第2のアクリル系エマルション(AEH−9)と市販の下記の粘着付与樹脂の水分散体とを表6−1に示す配合比で用いた以外は、実施例1と同様にして、水性感圧式接着剤および感圧式接着シートを作製し、評価した。
主な配合組成と評価結果を表6−1に示す。
(Comparative Examples 2 to 4)
In Comparative Example 2, instead of the first acrylic emulsion (AEL-1) and the second acrylic emulsion (AEH-1), the first acrylic emulsion (AEL-1) and the following commercially available adhesive are imparted. An aqueous pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were prepared and evaluated in the same manner as in Example 1 except that the aqueous dispersion of the resin was used in the compounding ratio shown in Table 6-1.
In Comparative Examples 3 and 4, instead of the first acrylic emulsion (AEL-1) and the second acrylic emulsion (AEH-1), the first acrylic emulsion (AEL-1) and the tackifier resin (AEL-1) were used. The same as in Example 1 except that the second acrylic emulsion (AEH-9) containing no TF) and the aqueous dispersion of the following tackifying resin on the market were used in the blending ratios shown in Table 6-1. A water-based pressure-sensitive adhesive and a pressure-sensitive adhesive sheet were prepared and evaluated.
Table 6-1 shows the main composition and evaluation results.
<粘着付与樹脂の水分散体>
(E−865)荒川化学製「スーパーエステル E−865」(重合ロジンエステルの水分散体、固形分50%、軟化点160℃)。
表中、「粘着付与樹脂の水分散体の配合量」は、第1のアクリル系エマルション(AEL)と第2のアクリル系エマルション(AEH)の総量100部に対する粘着付与樹脂の配合量である。
<Water dispersion of adhesive resin>
(E-865) "Super Ester E-865" manufactured by Arakawa Chemical Co., Ltd. (aqueous dispersion of polymerized rosin ester, solid content 50%, softening point 160 ° C.).
In the table, the "blending amount of the aqueous dispersion of the tackifier resin" is the blending amount of the tackifier resin with respect to 100 parts of the total amount of the first acrylic emulsion (AEL) and the second acrylic emulsion (AEH).
[評価項目と評価方法]
(ポリエチレン板に対する常温接着力)
23℃50%RH環境下にて、感圧式接着シートから剥離紙を剥がし、露出した感圧式接着層をポリエチレン板上に貼り付け、感圧式接着シート上で質量2kgのロ−ルを1往復させて、圧着した。その直後に接着力を測定した。この接着力を「常温接着力」と定義した。接着力は、JIS Z−0237に準拠し、剥離速度:300mm/分、剥離角180゜の条件で測定した。評価基準は以下の通りである。
常温接着力が10N/25mm以上。優良。
常温接着力が8N/25mm以上10N/25mm未満。良好。
常温接着力が6N/25mm以上8N/25mm未満。実用可。
常温接着力が6N/25mm未満。実用不可。
[Evaluation items and evaluation methods]
(Room temperature adhesive strength to polyethylene plate)
In a 23 ° C. and 50% RH environment, the release paper is peeled off from the pressure-sensitive adhesive sheet, the exposed pressure-sensitive adhesive layer is attached on a polyethylene plate, and a roll having a mass of 2 kg is reciprocated once on the pressure-sensitive adhesive sheet. And crimped. Immediately after that, the adhesive strength was measured. This adhesive force was defined as "normal temperature adhesive force". The adhesive strength was measured in accordance with JIS Z-0237 under the conditions of peeling speed: 300 mm / min and peeling angle of 180 °. The evaluation criteria are as follows.
Room temperature adhesive strength is 10N / 25mm or more. Excellent.
Room temperature adhesive strength is 8N / 25mm or more and less than 10N / 25mm. Good.
Room temperature adhesive strength is 6N / 25mm or more and less than 8N / 25mm. Practical use is possible.
Room temperature adhesive strength is less than 6N / 25mm. Not practical.
(ポリエチレン丸棒に対する曲面貼付性)
幅25mm、長さ100mmの感圧式接着シートから、幅20mm、長さ15mmの試験片を切り出した。試験片の長さ方向は、製造時のシートの流れ方向に合わせた。この試験片から剥離紙を剥がし、露出した感圧式接着層を、長さ30cm、直径10mmのポリエチレン製の丸棒の周囲に貼り付け、指で強く圧着した。このとき、試験片の幅方向(長手方向)とポリエチレン棒の長さ方向とを合わせた。上記試料を23℃雰囲気下にて7日間放置した後、試験片の剥離の有無を目視にて観察した。評価基準は以下の通りである。
◎:試験片の剥離なし。優良。
〇:試験片の両端部が端から2mm未満剥離。良好。
△:試験片の少なくとも一方の端部が端から2mm以上5mm未満剥離。実用可。
×:試験片の少なくとも一方の端部が端から5mm以上剥離。実用不可。
(Curved surface stickability to polyethylene round bar)
A test piece having a width of 20 mm and a length of 15 mm was cut out from a pressure-sensitive adhesive sheet having a width of 25 mm and a length of 100 mm. The length direction of the test piece was adjusted to the flow direction of the sheet at the time of manufacture. The release paper was peeled off from this test piece, and the exposed pressure-sensitive adhesive layer was attached around a polyethylene round bar having a length of 30 cm and a diameter of 10 mm, and strongly pressure-bonded with a finger. At this time, the width direction (longitudinal direction) of the test piece and the length direction of the polyethylene rod were aligned. After leaving the sample in an atmosphere of 23 ° C. for 7 days, the presence or absence of peeling of the test piece was visually observed. The evaluation criteria are as follows.
⊚: No peeling of test piece. Excellent.
〇: Both ends of the test piece are peeled off by less than 2 mm from the ends. Good.
Δ: At least one end of the test piece is peeled from the end by 2 mm or more and less than 5 mm. Practical use is possible.
X: At least one end of the test piece is peeled off by 5 mm or more from the end. Not practical.
(高温保持力)
感圧式接着シートから剥離紙を剥がした後、露出した感圧式接着層を試験板としてのステンレス板(SUS304)上に貼り付けた。このとき、貼付け領域は25mm×25mmとした。JIS Z 0237の保持力の測定法に準じて、80℃50%RHの条件下にて、試験片に1kgの荷重をかけ、24時間後の試験片の位置ズレ量(mm)を測定した。なお、試験片が落下した場合は、完全に落下するまでの時間(秒)を測定した。評価基準は以下の通りである。表には、試験片の位置ズレ量または試験片が落下するまでの時間(秒)を記載してある。
試験片の位置ズレ量が1.0mm未満。優良。
試験片の位置ズレ量が1.0mm以上5.0mm未満。良好。
試験片の位置ズレ量が5.0mm以上25.0mm未満。実用可。
試験片の位置ズレ量が25.0mm以上であり、試験片が落下。実用不可。
(High temperature holding power)
After peeling the release paper from the pressure-sensitive adhesive sheet, the exposed pressure-sensitive adhesive layer was attached on a stainless plate (SUS304) as a test plate. At this time, the sticking area was set to 25 mm × 25 mm. According to the method for measuring the holding force of JIS Z 0237, a load of 1 kg was applied to the test piece under the condition of 80 ° C. and 50% RH, and the amount of misalignment (mm) of the test piece after 24 hours was measured. When the test piece fell, the time (seconds) until it completely fell was measured. The evaluation criteria are as follows. The table shows the amount of misalignment of the test piece or the time (seconds) until the test piece falls.
The amount of misalignment of the test piece is less than 1.0 mm. Excellent.
The amount of misalignment of the test piece is 1.0 mm or more and less than 5.0 mm. Good.
The amount of misalignment of the test piece is 5.0 mm or more and less than 25.0 mm. Practical use is possible.
The amount of misalignment of the test piece is 25.0 mm or more, and the test piece falls. Not practical.
(ポリエチレン板に対する低温接着力)
感圧式接着シートおよび被着体としてのポリエチレン板を−10℃環境下に24時間放置した。その後、同じ温度条件下にて、感圧式接着シートから剥離紙を剥がし、露出した感圧式接着層をポリエチレン板上に貼り付け、感圧式接着シート上で質量2kgのロ−ルを1往復させて、圧着した。その直後に接着力を測定した。この接着力を「低温接着力」と定義する。接着力は、JIS Z−0237に準拠し、剥離速度:300mm/分、剥離角180゜の条件で測定した。評価基準は以下の通りである。
低温接着力が5N/25mm以上。優良。
低温接着力が4N/25mm以上5N/25mm未満。良好。
低温接着力が2N/25mm以上4N/25mm未満。実用可。
低温接着力が2N/25mm未満、実用不可。
(Low temperature adhesive force to polyethylene plate)
The pressure-sensitive adhesive sheet and the polyethylene plate as an adherend were left in an environment of −10 ° C. for 24 hours. Then, under the same temperature conditions, the release paper is peeled off from the pressure-sensitive adhesive sheet, the exposed pressure-sensitive adhesive layer is attached on the polyethylene plate, and a roll having a mass of 2 kg is reciprocated once on the pressure-sensitive adhesive sheet. , Crimped. Immediately after that, the adhesive strength was measured. This adhesive force is defined as "low temperature adhesive force". The adhesive strength was measured in accordance with JIS Z-0237 under the conditions of peeling speed: 300 mm / min and peeling angle of 180 °. The evaluation criteria are as follows.
Low temperature adhesive strength is 5N / 25mm or more. Excellent.
Low temperature adhesive strength is 4N / 25mm or more and less than 5N / 25mm. Good.
Low temperature adhesive strength is 2N / 25mm or more and less than 4N / 25mm. Practical use is possible.
Low temperature adhesive strength is less than 2N / 25mm, not practical.
(ヘーズ値)
コンマコーターを用いて、得られた水性感圧式接着剤を50μm厚のポリエチレンテレフタレート(PET)フィルム上に、乾燥後の膜の質量が25g/m2となるように塗工し、105℃の乾燥オーブンを用いて60秒間乾燥して、感圧式接着層を形成した。得られた積層体のヘーズ値を、HAZEメーターを用いて測定した。評価基準は以下の通りである。
ヘーズ値が6.0以上10.0以下、感圧式接着層に相分離が顕著に見られる。
ヘーズ値が5.0以上6.0未満、感圧式接着層に相分離が見られる。
ヘーズ値が5.0未満、感圧式接着層に相分離が明確に見られない。
(Haze value)
Using a comma coater, the obtained water-based pressure-sensitive adhesive was applied onto a 50 μm-thick polyethylene terephthalate (PET) film so that the weight of the film after drying was 25 g / m 2, and dried at 105 ° C. It was dried in an oven for 60 seconds to form a pressure-sensitive adhesive layer. The haze value of the obtained laminate was measured using a HAZE meter. The evaluation criteria are as follows.
The haze value is 6.0 or more and 10.0 or less, and phase separation is remarkably observed in the pressure-sensitive adhesive layer.
The haze value is 5.0 or more and less than 6.0, and phase separation is observed in the pressure-sensitive adhesive layer.
The haze value is less than 5.0, and phase separation is not clearly seen in the pressure-sensitive adhesive layer.
[結果のまとめ]
実施例1〜12では、
Tgが−70〜−40℃である第1のアクリル系共重合体(APL)を含む第1のアクリル系エマルション(AEL)と、
Tgが60〜120℃である第2のアクリル系共重合体(APH)と軟化点が130℃以上のロジン系樹脂である粘着付与樹脂(TF)とを含む第2のアクリル系エマルション(AEH)とを配合して、水性感圧式接着剤を製造した。
実施例1〜12では、得られた水性感圧式接着剤を用いて、感圧式接着シートを製造した。
[Summary of results]
In Examples 1-12,
A first acrylic emulsion (AEL) containing a first acrylic copolymer (APL) having a Tg of −70 to −40 ° C.
A second acrylic emulsion (AEH) containing a second acrylic copolymer (APH) having a Tg of 60 to 120 ° C. and a tackifier resin (TF) which is a rosin resin having a softening point of 130 ° C. or higher. And were blended to produce a water-based pressure-sensitive adhesive.
In Examples 1 to 12, a pressure-sensitive adhesive sheet was produced using the obtained water-based pressure-sensitive adhesive.
実施例1〜12で得られた感圧式接着シートはいずれも、常温接着力、曲面貼付性、高温保持力、および低温接着力が良好であった。これら実施例で得られた感圧式接着シートはいずれも、曲面形状を有する被着体、および接着が難しいポリオレフィン被着体に対しても、良好な接着力を有することが確認できた。これら実施例で得られた感圧式接着シートはいずれも、接着が難しいポリオレフィン被着体に対して、−10℃の低温でも、良好な接着力を有することが確認できた。
実施例1〜12の水性感圧式接着剤では、第1のアクリル系共重合体(APL)と第2のアクリル系共重合体(APH)との総量100質量部に対して、粘着付与樹脂(TF)の含有量は1.0質量部以上5.5質量部未満とした。粘着付与樹脂(TF)の含有量が少量でも、良好な結果が得られた。
All of the pressure-sensitive adhesive sheets obtained in Examples 1 to 12 had good room temperature adhesive strength, curved surface adhesiveness, high temperature holding power, and low temperature adhesive strength. It was confirmed that all of the pressure-sensitive adhesive sheets obtained in these examples had good adhesive strength even for an adherend having a curved surface shape and a polyolefin adherend which was difficult to adhere. It was confirmed that all of the pressure-sensitive adhesive sheets obtained in these examples had good adhesive strength with respect to the polyolefin adherend, which is difficult to adhere, even at a low temperature of −10 ° C.
In the water-based pressure-sensitive adhesives of Examples 1 to 12, the tackifier resin (adhesive-imparting resin) was applied to 100 parts by mass of the total amount of the first acrylic copolymer (APL) and the second acrylic copolymer (APH). The content of TF) was 1.0 part by mass or more and less than 5.5 parts by mass. Good results were obtained even with a small amount of tackifier resin (TF).
実施例1〜12ではいずれも、50μm厚のPETフィルム上に、乾燥質量25g/m2の条件で水性感圧式接着剤を塗工および乾燥して得られる積層体のヘーズ値が5.0〜10.0であり、感圧式接着層の相分離状態が良好であった。走査型プローブ顕微鏡観察を実施したところ、Tgが低く相対的に柔らかい第1のアクリル系共重合体(APL)を含むマトリクス相(海相)の中に、Tgが高く相対的に硬い第2のアクリル系共重合体(APH)と粘着付与樹脂(TF)とを含む相分離ドメイン(島相)が複数形成されている様子が確認された。代表として、実施例1の感圧式接着層の走査型プローブ顕微鏡写真を図1に示す。 In each of Examples 1 to 12, the haze value of the laminate obtained by applying and drying a water-based pressure-sensitive adhesive on a PET film having a thickness of 50 μm under the condition of a dry mass of 25 g / m 2 is 5.0 to 5. It was 10.0, and the phase-separated state of the pressure-sensitive adhesive layer was good. When the scanning probe microscope observation was carried out, the second acrylic phase (sea phase) containing the first acrylic copolymer (APL) having a low Tg and being relatively soft had a high Tg and was relatively hard. It was confirmed that a plurality of phase-separated domains (island phases) containing the acrylic copolymer (APH) and the tackifier resin (TF) were formed. As a representative, a scanning probe micrograph of the pressure-sensitive adhesive layer of Example 1 is shown in FIG.
粘着付与樹脂を使用しなかった比較例1で得られた感圧式接着シートは、常温接着力、曲面貼付性、および低温接着力が不良であった。 The pressure-sensitive adhesive sheet obtained in Comparative Example 1 in which no tack-imparting resin was used had poor room temperature adhesive strength, curved surface adhesiveness, and low temperature adhesive strength.
第2のアクリル系エマルション(AEH)を使用せず、第1のアクリル系エマルション(AEL)と粘着付与樹脂の水分散体とを配合した比較例2で得られた感圧式接着シートは、常温接着力および高温保持力が不良であった。
比較例2では、50μm厚のPETフィルム上に、乾燥質量25g/m2の条件で水性感圧式接着剤を塗工および乾燥して得られる積層体のヘーズ値が5.0未満であり、走査型プローブ顕微鏡観察を実施したが、感圧式接着層の相分離が明確に見られなかった。比較例2の感圧式接着層の走査型プローブ顕微鏡写真を図2に示す。
The pressure-sensitive adhesive sheet obtained in Comparative Example 2 in which the first acrylic emulsion (AEL) and the aqueous dispersion of the tackifier resin were blended without using the second acrylic emulsion (AEH) was bonded at room temperature. The force and high temperature holding power were poor.
In Comparative Example 2, the haze value of the laminate obtained by applying and drying the water-based pressure-sensitive adhesive on a PET film having a thickness of 50 μm under the condition of a dry mass of 25 g / m 2 was less than 5.0, and scanning was performed. A type probe microscope observation was carried out, but the phase separation of the pressure-sensitive adhesive layer was not clearly observed. A scanning probe micrograph of the pressure-sensitive adhesive layer of Comparative Example 2 is shown in FIG.
第1のアクリル系エマルション(AEL)と、粘着付与樹脂を含まない第2のアクリル系エマルション(AEH)と、粘着付与樹脂の水分散体とを配合した比較例3で得られた感圧式接着シートは、常温接着力が不良であった。
比較例3では、50μm厚のPETフィルム上に、乾燥質量25g/m2の条件で水性感圧式接着剤を塗工および乾燥して得られる積層体のヘーズ値が5.0未満であり、走査型プローブ顕微鏡観察を実施したが、感圧式接着層の相分離が明確に見られなかった(比較例2と同様)。
The pressure-sensitive adhesive sheet obtained in Comparative Example 3 in which the first acrylic emulsion (AEL), the second acrylic emulsion (AEH) containing no tackifier resin, and the aqueous dispersion of the tackifier resin were blended. The normal temperature adhesive strength was poor.
In Comparative Example 3, the haze value of the laminate obtained by applying and drying the water-based pressure-sensitive adhesive on a PET film having a thickness of 50 μm under the condition of a dry mass of 25 g / m 2 was less than 5.0, and scanning was performed. A type probe microscope observation was carried out, but phase separation of the pressure-sensitive adhesive layer was not clearly observed (similar to Comparative Example 2).
比較例4では、比較例3に対して粘着付与樹脂の水分散体の添加量を多くすることで、常温接着力と曲面貼付性を向上できたが、高温保持力と低温接着力が不良となった。 In Comparative Example 4, the normal temperature adhesive strength and the curved surface adhesiveness could be improved by increasing the amount of the water dispersion of the tackifier resin added as compared with Comparative Example 3, but the high temperature holding power and the low temperature adhesive strength were poor. became.
Tgが60℃未満の第2のアクリル系共重合体(APH)を用いた比較例5で得られた感圧式接着シートは、曲面貼付性と高温保持力が不良であった。
比較例5では、50μm厚のPETフィルム上に、乾燥質量25g/m2の条件で水性感圧式接着剤を塗工および乾燥して得られる積層体のヘーズ値が5.0未満であり、走査型プローブ顕微鏡観察を実施したが、感圧式接着層の相分離が明確に見られなかった(比較例2と同様)。
The pressure-sensitive adhesive sheet obtained in Comparative Example 5 using the second acrylic copolymer (APH) having a Tg of less than 60 ° C. had poor curved surface stickability and high-temperature holding power.
In Comparative Example 5, the haze value of the laminate obtained by applying and drying the water-based pressure-sensitive adhesive on a PET film having a thickness of 50 μm under the condition of a dry mass of 25 g / m 2 was less than 5.0, and scanning was performed. A type probe microscope observation was carried out, but phase separation of the pressure-sensitive adhesive layer was not clearly observed (similar to Comparative Example 2).
軟化点が130℃未満の粘着付与樹脂(TF)を含む第2のアクリル系エマルション(AEH)を用いた比較例6では、ポリオレフィン被着体に対する接着力が不良であった。 In Comparative Example 6 using the second acrylic emulsion (AEH) containing the tackifier resin (TF) having a softening point of less than 130 ° C., the adhesive force to the polyolefin adherend was poor.
非ロジン系の粘着付与樹脂(TF)を含む第2のアクリル系エマルション(AEH)を用いた比較例7、8で得られた感圧式接着シートは、曲面貼付性が不良であった。 The pressure-sensitive adhesive sheets obtained in Comparative Examples 7 and 8 using the second acrylic emulsion (AEH) containing a non-rosin-based tackifier resin (TF) had poor curved surface stickability.
本発明は上記実施形態及び実施例に限定されるものではなく、本発明の趣旨を逸脱しない限りにおいて、適宜設計変更が可能である。 The present invention is not limited to the above-described embodiments and examples, and the design can be appropriately changed as long as the gist of the present invention is not deviated.
Claims (9)
ガラス転移温度が相対的に高い第2のアクリル系共重合体(APH)と粘着付与樹脂とを含む第2のアクリル系エマルション(AEH)とを含む水性感圧式接着剤であって、
第1のアクリル系共重合体(APL)のガラス転移温度が−70〜−40℃であり、
第2のアクリル系共重合体(APH)のガラス転移温度が60〜120℃であり、
前記粘着付与樹脂は、軟化点が130℃以上のロジン系樹脂である、水性感圧式接着剤。 A first acrylic emulsion (AEL) containing a first acrylic copolymer (APL) having a relatively low glass transition temperature, and
A water-based pressure-sensitive adhesive containing a second acrylic copolymer (APH) having a relatively high glass transition temperature and a second acrylic emulsion (AEH) containing a tackifier resin.
The glass transition temperature of the first acrylic copolymer (APL) is −70 to −40 ° C.
The glass transition temperature of the second acrylic copolymer (APH) is 60 to 120 ° C.
The tackifier resin is a water-based pressure-sensitive adhesive which is a rosin-based resin having a softening point of 130 ° C. or higher.
ガラス転移温度が相対的に高い第2のアクリル系共重合体(APH)と粘着付与樹脂とを含む第2のアクリル系エマルション(AEH)とを含む水性感圧式接着剤の製造方法であって、
複数種のエチレン性不飽和単量体を乳化重合して、ガラス転移温度が−70〜−40℃である第1のアクリル系共重合体(APL)を含む第1のアクリル系エマルション(AEL)を製造する工程(1)と、
乳化剤と、軟化点が130℃以上のロジン系樹脂である粘着付与樹脂との存在下で、複数種のエチレン性不飽和単量体を乳化重合して、ガラス転移温度が60〜120℃である第2のアクリル系共重合体(APH)を含む第2のアクリル系エマルション(AEH)を製造する工程(2)と、
第1のアクリル系エマルション(AEL)と第2のアクリル系エマルション(AEH)とを混合する工程(3)とを有する、水性感圧式接着剤の製造方法。 A first acrylic emulsion (AEL) containing a first acrylic copolymer (APL) having a relatively low glass transition temperature, and
A method for producing an aqueous pressure-sensitive adhesive containing a second acrylic copolymer (APH) having a relatively high glass transition temperature and a second acrylic emulsion (AEH) containing a tackifier resin.
A first acrylic emulsion (AEL) containing a first acrylic copolymer (APL) having a glass transition temperature of −70 to −40 ° C. by emulsion polymerization of a plurality of types of ethylenically unsaturated monomers. (1) and
In the presence of an emulsifier and a tackifier resin which is a rosin-based resin having a softening point of 130 ° C. or higher, a plurality of types of ethylenically unsaturated monomers are emulsion-polymerized and the glass transition temperature is 60 to 120 ° C. The step (2) of producing a second acrylic emulsion (AEH) containing the second acrylic copolymer (APH), and
A method for producing a water-based pressure-sensitive adhesive, which comprises a step (3) of mixing a first acrylic emulsion (AEL) and a second acrylic emulsion (AEH).
前記複数種のエチレン性不飽和単量体中に前記粘着付与樹脂を溶解させる工程(2−a)と、
工程(2−a)で得られた混合溶液を、乳化剤および水の存在下で強制乳化させて、油溶成分の平均粒子径が0.3〜2.0μmである乳化物を得る工程(2−b)と、
前記乳化物を乳化重合する工程(2−c)とを含む、
請求項8に記載の水性感圧式接着剤の製造方法。 Step (2) is
In the step (2-a) of dissolving the tackifier resin in the plurality of types of ethylenically unsaturated monomers,
The mixed solution obtained in step (2-a) is forcibly emulsified in the presence of an emulsifier and water to obtain an emulsion having an average particle size of an oil-soluble component of 0.3 to 2.0 μm (2). −B) and
The step (2-c) of emulsion polymerization of the emulsion is included.
The method for producing a water-based pressure-sensitive adhesive according to claim 8.
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