JP2018095829A - Adhesive composition and laminate using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an adhesive composition whose cured product exhibits excellent adhesion, thermal shock resistance, and moist heat resistance.SOLUTION: The adhesive composition contains, based on A) 100 pts.mass of a polyfunctional thiol compound having 2-6 thiol groups, B) 5-25 pts.mass of a polyfunctional (meth)acrylate having 2-6 (meth)acrylic groups, C) 80-200 pts.mass of a urethane (meth)acrylate having a specific structure and having a weight-average molecular weight of 1,000-15,000, D) 30-150 pts.mass of a monofunctional (meth)acrylate having only one (meth)acrylic group, and E) 5-25 pts.mass of a hydroxyl group-containing (meth)acrylamide.SELECTED DRAWING: None

Description

  The present invention relates to a pressure-sensitive adhesive composition whose cured product is excellent in adhesion and flexibility and has high durability, and further relates to a laminate using the pressure-sensitive adhesive composition.

  Adhesives are used in various applications such as tapes and labels. In the field of electro-optical devices, adhesives with high adhesion and transparency are used to attach panels and optical members such as optical filters, sensors, and front plates. It is used for matching. In recent years, in-vehicle electro-optical devices such as car navigation systems have been required to have a much higher thermal shock resistance for adhesives than indoor electro-optical devices such as televisions. This is because in-vehicle devices are exposed to a considerably high temperature in the vehicle for a long time during the day and, on the contrary, a considerably low temperature at night. For this reason, in general, when an adhesive used for a polarizing plate or a front plate of an indoor TV is used for an in-vehicle device, it cannot be said that the thermal shock resistance to a severe temperature change is necessarily sufficient, and peeling may occur. there were.

  In addition, in a vehicle-mounted device, a transparent resin plate is increasingly used for reducing the weight of the front plate and improving the design. However, when the resin plate is placed under high temperature and high humidity, outgas is released from the inside of the resin plate, and bubbles are formed by the gas in the interface between the resin plate and the adhesive and in the adhesive composition, and visibility is reduced. There is also a problem of heat and moisture resistance.

  Conventionally, as a technique for improving the heat-and-moisture resistance of a pressure-sensitive adhesive, a technique for increasing the Tg of the pressure-sensitive adhesive by using urethane acrylate exhibiting a high glass transition temperature (Tg) is known (see Patent Document 1). However, when the Tg of the pressure-sensitive adhesive is increased, the pressure-sensitive adhesive becomes hard, the flexibility is deteriorated, and the pressure-sensitive adhesive follows the difference in thermal expansion of the bonded resin plates in the thermal shock test assuming temperature change in the vehicle. There was a problem that peeling could occur without being able to. Moreover, the improvement of heat-and-moisture resistance was not necessarily sufficient.

JP 2013-35920 A

  The present invention has been accomplished in view of the above circumstances, and the object thereof is a pressure-sensitive adhesive composition having a high adhesiveness, thermal shock resistance, and heat-and-moisture resistance, and a pressure-sensitive adhesive comprising the pressure-sensitive adhesive composition. It is to provide a laminate having layers.

（式中のａは１〜１５の整数である。Ｒ^１は炭素数１〜１４の炭化水素基であり、Ｒ^２は炭素数１〜１４の炭化水素基、下記式２で表されるポリエーテル基、又は下記式３で表されるポリエステル基であり、Ｒ^３は水素原子又はメチル基であり、Ｒ^４は炭素数１〜１４の炭化水素基である。）

（式中のｂは１〜２０の整数である。Ｒ^５はそれぞれ独立した炭素数２〜１４の炭化水素基）

（式中のｃは１〜２０の整数である。Ｒ^６及びＲ^７は炭素数１〜１４の炭化水素基であり、それぞれ同一であっても異なっていても良い。） The pressure-sensitive adhesive composition of the present invention comprises (A) a polyfunctional thiol compound having 2 to 6 thiol groups, (B) a polyfunctional (meth) acrylate having 2 to 6 (meth) acryl groups, and (C ) Urethane (meth) acrylate having a weight average molecular weight of 1000 to 15000 represented by the following formula 1, (D) monofunctional (meth) acrylate having only one (meth) acryl group, and (E) hydroxyl group-containing When the polyfunctional thiol compound containing (meth) acrylamide and having (A) 2 to 6 thiol groups is 100 parts by mass, 5 to 25 parts by mass of (B) polyfunctional (meth) acrylate, (C ) 80-200 parts by mass of urethane (meth) acrylate, (D) 30-150 parts by mass of monofunctional (meth) acrylate having only one (meth) acrylic group, (E) containing hydroxyl group (Meth) acrylamide in a proportion of 5 to 25 parts by weight.

(In the formula, a is an integer of ¹ to 15. R ¹ is a hydrocarbon group having 1 to 14 carbon atoms, R ² is a hydrocarbon group having 1 to 14 carbon atoms, and poly represented by the following formula 2. An ether group or a polyester group represented by the following formula 3, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrocarbon group having 1 to 14 carbon atoms.)

(In the formula, b is an integer of 1 to 20. R ⁵ is an independent hydrocarbon group having 2 to 14 carbon atoms.)

(In the formula, c is an integer of 1 to 20. R ⁶ and R ⁷ are each a hydrocarbon group having 1 to 14 carbon atoms, which may be the same or different.)

（式中のｄは２又は３であり、ｅは０又は１であり、ｆは１又は２であり、ｄとｅとｆの和は４である。Ｒ^８は、メチレン基、エチレン基又はイソプロピレン基であり、Ｒ^９は、下記式５又は式６で表される２価の官能基であり、Ｒ^１０は、メチル基又はエチル基であり、Ｒ^１１は、炭素数が１〜１２の炭化水素基である。）

（式中のＲ^１２は水素原子又はメチル基である。）

（式中のＲ^１３は水素原子又はメチル基である。） The (A) polyfunctional thiol compound having 2 to 6 thiol groups is preferably a polyfunctional thiol compound represented by the following formula 4.

(In the formula, d is 2 or 3, e is 0 or 1, f is 1 or 2, and the sum of d, e, and f is 4. R ⁸ is a methylene group, an ethylene group, or It is an isopropylene group, R ⁹ is a divalent functional group represented by the following formula 5 or 6, R ¹⁰ is a methyl group or an ethyl group, and R ¹¹ has 1 to 12 carbon atoms. Hydrocarbon group.)

(In the formula, R ¹² is a hydrogen atom or a methyl group.)

(In the formula, R ¹³ is a hydrogen atom or a methyl group.)

（式中のｇは２〜５の整数であり、ｈは０〜２の整数であり、ｉは１〜４の整数であり、ｇとｈとｉの和は６である。Ｒ^１４は下記式８で表される６価の官能基であり、Ｒ^１５は、メチレン基、エチレン基又はイソプロピレン基であり、Ｒ^１６は、下記式５又は式６で表される２価の官能基であり、Ｒ^１７は、メチル基又はエチル基であり、Ｒ^１８は、炭素数が１〜１２の炭化水素基である。）

（式中のＲ^１２は水素原子又はメチル基である。）

（式中のＲ^１３は水素原子又はメチル基である。）

The (A) polyfunctional thiol compound having 2 to 6 thiol groups is preferably a polyfunctional thiol compound represented by the following formula 7.

(In the formula, g is an integer of 2 to 5, h is an integer of 0 to 2, i is an integer of 1 to 4, and the sum of g, h, and i is 6. R ¹⁴ is the following. It is a hexavalent functional group represented by Formula 8, R ¹⁵ is a methylene group, ethylene group or isopropylene group, and R ¹⁶ is a divalent functional group represented by Formula 5 or Formula 6 below. Yes, R ¹⁷ is a methyl group or an ethyl group, and R ¹⁸ is a hydrocarbon group having 1 to 12 carbon atoms.)

(In the formula, R ¹² is a hydrogen atom or a methyl group.)

(In the formula, R ¹³ is a hydrogen atom or a methyl group.)

（式中のＲ^１９は下記式１０で表される３価の官能基であり、Ｒ^２０は下記式５又は式６で表される２価の官能基であり、Ｒ^２１は炭素数が１〜１２の炭化水素基である。）

（式中のＲ^２２はメチレン基、エチレン基又はイソプロピレン基である。）

（式中のＲ^１２は水素原子又はメチル基である。）

（式中のＲ^１３は水素原子又はメチル基である。） The (A) polyfunctional thiol compound having 2 to 6 thiol groups is preferably a polyfunctional thiol compound represented by the following formula 9.

(In the formula, R ¹⁹ is a trivalent functional group represented by the following formula 10, R ²⁰ is a divalent functional group represented by the following formula 5 or 6, and R ²¹ has 1 carbon atom. ˜12 hydrocarbon groups.)

(In the formula, R ²² is a methylene group, an ethylene group or an isopropylene group.)

(In the formula, R ¹² is a hydrogen atom or a methyl group.)

(In the formula, R ¹³ is a hydrogen atom or a methyl group.)

  In the laminate of the present invention, an uncured adhesive layer made of the above-mentioned adhesive composition is laminated on one surface of a transparent substrate.

  In the laminate of the present invention, an uncured adhesive layer made of the above-mentioned adhesive composition and a substrate are laminated in this order on one surface of a transparent substrate.

  In the laminate of the present invention, the pressure-sensitive adhesive layer obtained by curing the pressure-sensitive adhesive composition and the base material are laminated in this order on one surface of the transparent base material.

  In the present invention, “(meth) acrylate” means a generic name including both acrylate and methacrylate, and the same applies to “(meth) acrylamide”, “(meth) acryl group”, and the like. In the present invention, “XX to XX” indicating a numerical range is a concept including a lower limit (XX) and an upper limit (XX) unless otherwise specified. In other words, it means “more than XX and less than xx”. “Molecular weight” means a weight average molecular weight unless otherwise specified.

  This invention can provide the laminated body which has the adhesion layer which the hardened | cured material has high adhesiveness, thermal shock resistance, and heat-and-moisture resistance, and the adhesive layer which consists of the said adhesive composition.

  In the pressure-sensitive adhesive composition of the present invention, the moisture barrier property is improved by forming a precise crosslinked network by the addition reaction of polyfunctional thiol, polyfunctional (meth) acrylate, and urethane (meth) acrylate. Therefore, even if the cured product is exposed to a high-humidity atmosphere, water can be prevented from entering. Moreover, since the bond angle and bond length of the thioether bond generated by the thiol-ene reaction can be changed flexibly compared to the bond of atoms such as C, O, and N, the cured product has excellent flexibility (thermal shock resistance), Excellent adhesion to the substrate.

  Furthermore, by adding hydroxyl group-containing (meth) acrylamide, hydroxyl groups and acrylamide groups capable of hydrogen bonding are introduced onto the crosslinking network, and the crosslinking density can be increased efficiently through hydrogen bonding in the crosslinking network. . In addition, since crosslinking by hydrogen bonding does not lower the flexibility of the cured product as compared with covalent bonding, moisture barrier properties and toughness can be enhanced while maintaining high thermal shock resistance.

  In addition, since water tends to collect in the vicinity of hydroxyl groups under high temperature and high humidity, even if water enters under high temperature and high humidity, the intruded water is captured by hydrogen bonds of hydroxyl group-containing (meth) acrylamide. Since the acrylamide group is less likely to be hydrolyzed than the (meth) acryl group, the composition is not easily deteriorated even under high temperature and high humidity. Thereby, even if it puts on more severe high temperature and high humidity, deterioration of a composition does not occur easily and it can improve heat-and-moisture resistance.

  In other words, since a precise cross-linking network is formed by the addition reaction of polyfunctional thiol and polyfunctional (meth) acrylate, even a small amount of hydroxyl group-containing (meth) acrylamide can efficiently increase the cross-linking density and flexibility. Can exhibit significantly superior durability (moisture and heat resistance) without losing the weight.

  As a result, the pressure-sensitive adhesive composition of the present invention has excellent adhesion and flexibility (thermal shock resistance) in a cured product, and can realize high durability (moisture heat resistance).

  In the following, the present invention will be described in detail. The pressure-sensitive adhesive composition of the present invention comprises (A) a polyfunctional thiol compound having 2 to 6 thiol groups, (B) a polyfunctional (meth) acrylate, (C) a urethane (meth) acrylate, and (D) (meth). A monofunctional (meth) acrylate having only one acrylic group and (E) a hydroxyl group-containing (meth) acrylamide are essential components.

<(A) Polyfunctional thiol compound having 2 to 6 thiol groups>
(A) The polyfunctional thiol compound having 2 to 6 thiol groups may be a compound having 2 to 6 thiol groups at the terminal, and is represented by the above formula 4, formula 7, or formula 9, among others. Thioether-containing (meth) acrylate derivatives are preferred. A polyfunctional thiol compound can also be used individually by 1 type, and can also use 2 or more types together.

  When the pressure-sensitive adhesive composition contains (A) a polyfunctional thiol compound having 2 to 6 thiol groups, curing shrinkage is reduced, and the adhesiveness of the cured product can be improved. Moreover, since the adhesiveness of hardened | cured material becomes higher when five or less thiol groups are preferable. On the other hand, a polyfunctional thiol having 7 or more thiol groups is not preferable because the crosslink density is high and the curing shrinkage is increased, whereby the adhesiveness of the cured product is lowered. Further, the thioether-containing (meth) acrylate derivative represented by the above formula 4, formula 7, or formula 9 has a partial thiol group modified and an alkyl chain is introduced at the terminal. For this reason, the alkyl chain serves as a spacer, and the distance between the cross-linking points is increased, resulting in a more flexible structure. Thereby, the thermal shock resistance of the hardened | cured material of an adhesive composition can be improved more. Furthermore, the thioether-containing (meth) acrylate derivative represented by the above formula 4, formula 7, or formula 9 tends to form a crosslinked network in the entire cured product of the pressure-sensitive adhesive composition, and the cured product has better moisture and heat resistance. Show.

In the thioether-containing (meth) acrylate derivative represented by the above formula 4, the sum of d, e and f in the formula is 4, d is 2 or 3, respectively, e is 0 or 1, and f is 1 or 2. When the number of thiol groups is large, the crosslinkability by photoreaction increases, so d is preferably 3 when it is desired to accelerate the curing reaction or to improve the solvent resistance. Further, since the thioether group has a lower hydrophilicity than the thiol group, f is preferably 2 when it is desired to improve the compatibility with a highly hydrophobic solvent or to improve the adhesion of the cured product. In the above formula 4, R ⁸ is a methylene group, ethylene group or isopropylene group, and R ⁹ is a divalent functional group represented by the above formula 5 or formula 6. When R ⁹ is a functional group represented by the above formula 5, the adhesion of the cured product can be further improved, and when the functional group is represented by the above formula 6, the durability of the cured product is further improved. Can do. R ¹⁰ in the above formula 5 is a methyl group or an ethyl group, and R ¹¹ is a hydrocarbon group having 1 to 12 carbon atoms, preferably 2 to 12 carbon atoms, more preferably a carbon number. Is 4-12.

In the thioether-containing (meth) acrylate derivative represented by the formula 7, the sum of g, h and i in the formula is 6, each g is an integer of 2 to 5, and h is an integer of 0 to 2. Yes, i is an integer from 1 to 4. R ^{14 in} Formula 7 has a structure represented by Formula 8 above. When the number of thiol groups is large, the crosslinkability due to the photoreaction increases, and therefore g is preferably 5 when it is desired to accelerate the curing reaction or to improve the solvent resistance. Further, since the thioether group has a lower hydrophilicity than the thiol group, i is preferably 4 when it is desired to improve the compatibility with a solvent having high hydrophobicity or to improve the adhesion of the cured product. In the above formula 7, R ¹⁵ is a methylene group, ethylene group or isopropylene group, and R ¹⁶ is a divalent functional group represented by the above formula 5 or formula 6. When R ¹⁶ is a functional group represented by the above formula 5, the adhesion of the cured product can be further improved, and when it is a functional group represented by the above formula 6, the durability of the cured product is further improved. Can do. R ¹⁷ in the above formula 7 is a methyl group or an ethyl group, and R ¹⁸ is a hydrocarbon group having 1 to 12 carbon atoms, preferably 2 to 12 carbon atoms, and more preferably a carbon number. Is 4-12.

In the thioether-containing (meth) acrylate derivative represented by the above formula 9, R ¹⁹ has a structure having an isocyanurate ring represented by the above formula 10. The thioether-containing (meth) acrylate derivative represented by the above formula 9 is preferable in that the flexibility can be further improved. R ²⁰ in the above formula 9 is a divalent functional group represented by the above formula 5 or 6, and R ²¹ is a hydrocarbon group having 1 to 12 carbon atoms, preferably 2 to 12 carbon atoms. More preferably, it has 4 to 12 carbon atoms.

（式中のjは２〜６の整数である。Ｒ^２３は水素原子又はメチル基であり、Ｒ^２４は炭素数２〜１４の炭化水素基、炭素数２〜１４のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基、又はイソシアヌレート環と炭化水素基のみからなる基である。）
上記式１１中のＲ^２３が水素原子の場合、チオールとの反応性に優れるため、粘着剤組成物は硬化性に優れる。一方、Ｒ^２３がメチル基の場合、チオールとの反応性が劣るため、粘着剤組成物は貯蔵安定性の観点で優れる。また、（Ｂ）成分として式１１で表される化合物を用いる場合、Ｒ^２４の官能基の種類によって粘着剤組成物の硬化物の性質を更に向上できる。具体的には、Ｒ^２４が炭素数２〜１２の炭化水素基の場合には密着性が向上し、炭素数が４〜９であると向上効果がより高いため更に好ましい。Ｒ^２４が炭素数２〜１２のエーテル酸素と炭化水素基のみからなる基の場合には柔軟性が向上し、炭素数が４〜９であると向上効果がより高いため更に好ましい。Ｒ^２４がイソシアヌレート環と炭素数１〜３の炭化水素基のみからなる基の場合には耐久性が向上し、炭素数が２又は３であると向上効果がより高いため更に好ましい。 <(B) Polyfunctional (meth) acrylate having 2 to 6 (meth) acrylic groups>
(B) As a preferred example of a polyfunctional (meth) acrylate having 2 to 6 (meth) acrylic groups, a compound represented by the following formula 11 may be mentioned. When the pressure-sensitive adhesive composition contains (B) a polyfunctional (meth) acrylate, the heat-and-moisture resistance of the pressure-sensitive adhesive composition can be improved. On the other hand, when (B) polyfunctional (meth) acrylate has 7 or more (meth) acryl groups, the adhesiveness of the cured product is lowered, which is not preferable. In addition, the polyfunctional (meth) acrylate which is (B) component can also be used individually by 1 type, and can also use 2 or more types together.

(In the formula, j is an integer of 2 to 6. R ²³ is a hydrogen atom or a methyl group, R ²⁴ is a hydrocarbon group having 2 to 14 carbon atoms, ether oxygen having 2 to 14 carbon atoms (—O— ) And a hydrocarbon group alone, or a group consisting only of an isocyanurate ring and a hydrocarbon group.)
When R ²³ in the above formula 11 is a hydrogen atom, is excellent in reactivity with thiol, pressure-sensitive adhesive composition is excellent in curability. On the other hand, if R ²³ is a methyl group, since the reactivity with thiols poor pressure-sensitive adhesive composition is excellent in terms of storage stability. In addition, it further improves the properties of the cured product of the adhesive composition optionally, the type of the functional group of R ²⁴ using the compound of formula 11 as the component (B). Specifically, when R ²⁴ is a hydrocarbon group having 2 to 12 carbon atoms, adhesion is improved, and when the number of carbon atoms is 4 to 9, the improvement effect is higher, which is more preferable. In the case where R ²⁴ is a group consisting only of ether oxygen having 2 to 12 carbon atoms and a hydrocarbon group, the flexibility is improved, and when the number of carbon atoms is 4 to 9, the improvement effect is higher, which is further preferable. In the case where R ²⁴ is a group consisting only of an isocyanurate ring and a hydrocarbon group having 1 to 3 carbon atoms, durability is improved, and if the number of carbon atoms is 2 or 3, the improvement effect is higher, which is further preferable.

  Moreover, as (B) polyfunctional (meth) acrylate, a polymer type thing can also be used conveniently. As a polymer type polyfunctional (meth) acrylate, a (meth) acrylate having an epoxy group such as glycidyl (meth) acrylate or a copolymer has a group that reacts with an epoxy group such as (meth) acrylic acid. Polymer obtained by reacting (meth) acrylate, (meth) acrylate having hydroxyl group such as hydroxyethyl (meth) acrylate or copolymer, hydroxyl group such as 2-methylpropenoic acid 2-isocyanatoethyl A polymer obtained by reacting a (meth) acrylate having a group that reacts with carboxylic acid, a (meth) acrylate having a carboxyl group such as (meth) acrylic acid or a copolymer, a carboxyl group such as glycidyl (meth) acrylate (Meth) actyl having a group that reacts with Polymers obtained by reacting the rate and the like. Preferably, it is a polyfunctional (meth) acrylate having 2 to 4 (meth) acryl groups, for example, glycerin dimethacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, bisphenol A diglycidyl ether acrylic acid adduct Phenol novolac type diglycidyl ether acrylic acid adduct, bisphenol A diglycidyl ether methacrylic acid adduct, and the like can be used.

<(C) Urethane (meth) acrylate>
The urethane (meth) acrylate as the component (C) is a compound represented by the above formula 1, a diisocyanate compound represented by the following formula 12, a diol compound represented by the following formula 13, and a formula 14 below. Can be obtained by reaction with a (meth) acrylate compound having a hydroxyl group. When the pressure-sensitive adhesive composition contains (C) urethane (meth) acrylate, the coating property of the pressure-sensitive adhesive composition on the base material is improved, and the cohesive strength and stickiness of the cured product of the pressure-sensitive adhesive composition are improved. It is possible to increase the adhesion. In addition, urethane (meth) acrylate which is (C) component can also be used individually by 1 type, and can also use 2 or more types together.

In the above formula 1, R ¹ is a hydrocarbon group having 1 to 14 carbon atoms, preferably 4 to 13 carbon atoms. R ² is a hydrocarbon group having 1 to 14 carbon atoms, a polyether group represented by the above formula 2, or a polyester group represented by the above formula 3. When R ² is a hydrocarbon group, the carbon number is 2 to 12 are preferred, 4-9 is more preferable. R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrocarbon group having 1 to 14 carbon atoms. The number of carbon atoms in R ⁴ is 2 to 12 are preferred, 4-9 is more preferable. Moreover, R < ⁵ > in the said Formula 2 is a C2-C14 hydrocarbon group which was respectively independent, and C2-C8 is preferable and 2-6 are more preferable. R ⁶ and R ⁷ in the above formula 3 are hydrocarbon groups having 1 to 14 carbon atoms, which may be the same or different. The number of carbon atoms in the hydrocarbon group R ⁶ is 2 to 12 are preferred, more preferably 2 to 8. The number of carbon atoms in the hydrocarbon group R ⁷ is 2-6 preferably 2-4 more preferred.

（Ｒ^１は炭素数１〜１４の炭化水素基である。）
式１２中のＲ¹は炭素数４〜１３が好ましい。

（Ｒ^２は炭素数１〜１４の炭化水素基、上記式２で表されるポリエーテル基、又は上記式３で表されるポリエステル基である。）
式１３中のＲ^２が炭化水素基の場合、炭素数は２〜１２が好ましく、更に好ましくは、４〜９である。

（Ｒ^３は水素原子又はメチル基であり、Ｒ^４は炭素数１〜１４の炭化水素基である。）
式１４中のＲ^４の炭素数は２〜１２が好ましく、更に好ましくは４〜９である。

(R ¹ is a hydrocarbon group having 1 to 14 carbon atoms.)
R ^{1 in} Formula 12 preferably has 4 to 13 carbon atoms.

(R ² is a hydrocarbon group having 1 to 14 carbon atoms, a polyether group represented by Formula 2 above, or a polyester group represented by Formula 3 above.)
When R ^{2 in} Formula 13 is a hydrocarbon group, the number of carbon atoms is preferably 2 to 12, more preferably 4 to 9.

(R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrocarbon group having 1 to 14 carbon atoms.)
The number of carbon atoms of ^{R 4} in the formula 14 is 2 to 12 are preferred, more preferably from 4 to 9.

  As a diisocyanate compound represented by Formula 12, a known compound can be used, and it can also be used independently and can also use 2 or more types together.

  As a diol compound represented by Formula 13, a diol having 1 to 14 carbon atoms, a polyether diol, and a polyester diol can be used, and each can be used alone, or two or more types can be used. It can also be used together.

  As the (meth) acrylate compound having a hydroxyl group represented by Formula 14, a known compound can be used.

  (C) 1000-15000 is preferable from a viewpoint that the weight average molecular weight of urethane (meth) acrylate can express the ease of handling, the applicability | paintability of an adhesive composition, and the outstanding adhesiveness. When the weight average molecular weight is less than 1000, the cohesive force of the cured product is lowered and the adhesion is lowered. On the other hand, when the weight average molecular weight is larger than 15000, it is difficult to handle because the viscosity is high, and the coating property of the pressure-sensitive adhesive composition is also deteriorated.

（式中のＲ^２５は水素原子又はメチル基であり、Ｒ^２６は炭素数１〜２０の炭化水素基、炭素数１〜１４のエーテル酸素（−Ｏ−）と炭化水素基のみからなる基、１つ若しくは複数のヒドロキシル基が置換した炭素数１〜１４の炭化水素基、又は置換若しくは非置換のフェニル基である。）
式１５中のＲ^２６が炭化水素基の場合、炭素数は２〜１２が好ましく、４〜１２が更に好ましい。Ｒ^２６がエーテル酸素と炭化水素基のみからなる基の場合、炭素数は２〜１２が好ましく、４〜９が更に好ましい。Ｒ^２６が１つ若しくは複数のヒドロキシル基が置換した炭化水素基の場合、炭素数は２〜１２が好ましく、４〜１２が更に好ましい。 <Monofunctional (meth) acrylate having only one (D) (meth) acrylic group>
(D) The monofunctional (meth) acrylate having only one (meth) acryl group is a compound having only one (meth) acryl group in the molecule, and a preferred example thereof is a compound represented by the following formula 15. Is mentioned. The pressure-sensitive adhesive composition can improve thermal shock resistance by containing a monofunctional (meth) acrylate having only one (D) (meth) acryl group. In addition, the monofunctional (meth) acrylate which has only one (meth) acryl group which is (D) component can also be used individually by 1 type, and can also use 2 or more types together.

(In the formula, R ²⁵ is a hydrogen atom or a methyl group, R ²⁶ is a hydrocarbon group having 1 to 20 carbon atoms, a group consisting only of ether oxygen (—O—) having 1 to 14 carbon atoms and a hydrocarbon group, It is a C1-C14 hydrocarbon group substituted by one or more hydroxyl groups, or a substituted or unsubstituted phenyl group.)
When R ^{26 in} Formula 15 is a hydrocarbon group, the number of carbon atoms is preferably 2 to 12, and more preferably 4 to 12. When R ²⁶ is a group consisting only of ether oxygen and a hydrocarbon group, the number of carbon atoms is preferably 2 to 12, and more preferably 4 to 9. When R ²⁶ is a hydrocarbon group substituted with one or more hydroxyl groups, the number of carbon atoms is preferably 2 to 12, and more preferably 4 to 12.

（Ｒ^２７は水素原子又はメチル基であり、Ｒ^２８は炭素数１〜４の炭化水素基である。）
式１６中のＲ^２８が炭素数１〜３の炭化水素基の場合、硬化物のバリア性が高く、より優れた耐久性が実現できるため更に好ましい。 <(E) Hydroxyl group-containing (meth) acrylamide>
(E) Hydroxyl group-containing (meth) acrylamide is a compound containing a hydroxyl group in the molecule and having only one acrylamide group, and a preferred example thereof is a compound represented by the following formula 16. By including (E) hydroxyl group-containing (meth) acrylamide, the pressure-sensitive adhesive composition can improve the heat and moisture resistance of the cured product of the pressure-sensitive adhesive composition. This is because even if moisture enters the cured product under high temperature and high humidity, the moisture collects in the vicinity of the hydroxyl group and is captured by the hydrogen bond of the hydroxyl group-containing (meth) acrylamide. Since the (meth) acrylamide group is difficult to hydrolyze, it can retain moisture without being hydrolyzed by the trapped moisture, and consequently suppresses the dispersion of moisture and suppresses degradation due to hydrolysis of other components. Therefore, the heat and humidity resistance is improved. On the other hand, when (meth) acrylamide that does not contain a hydroxyl group is used, it becomes difficult for the (meth) acrylamide group to capture moisture, resulting in hydrolysis of other components, resulting in a decrease in wet heat resistance. In addition, the hydroxyl group containing (meth) acrylamide which is (E) component can also be used individually by 1 type, and 2 or more types can also be mixed and used for it.

^{(R 27} is a hydrogen atom or a methyl ^{group, R 28} is a hydrocarbon group having 1 to 4 carbon atoms.)
When R ^{28 in} Formula 16 is a hydrocarbon group having 1 to 3 carbon atoms, the cured product has a high barrier property, and more excellent durability can be realized.

<Additives>
In the pressure-sensitive adhesive composition, a photopolymerization initiator that improves the curability of the pressure-sensitive adhesive composition by an active energy ray such as ultraviolet (UV), absorbs ultraviolet light (UV), and cures the pressure-sensitive adhesive composition. UV stabilizers that improve the light resistance of cured products, light stabilizers and pressure-sensitive adhesive compositions that capture radicals generated in the cured products obtained by curing the adhesive composition and improve the light resistance of the cured products Additives such as a polymerization inhibitor that improves the storage stability of the product and a tackifier that improves the adhesion of the cured product obtained by curing the pressure-sensitive adhesive composition can be added.

<Composition ratio (mixing balance)>
In the pressure-sensitive adhesive composition of the present invention, (A) 5 to 25 parts by mass of (B) polyfunctional (meth) acrylate and (C) urethane with respect to 100 parts by mass of the polyfunctional thiol compound having 2 to 6 thiol groups. 80 to 200 parts by weight of (meth) acrylate, 30 to 150 parts by weight of monofunctional (meth) acrylate having only one (D) (meth) acryl group, and (E) 5 to 5 moles of hydroxyl group-containing (meth) acrylamide. It mix | blends so that it may become a ratio of 25 mass parts. (B) When the compounding quantity of polyfunctional (meth) acrylate is less than 5 mass parts, the toughness of hardened | cured material falls and it exists in the tendency for heat-and-moisture resistance to fall. (B) When the compounding quantity of polyfunctional (meth) acrylate exceeds 25 mass parts, it exists in the tendency for the softness | flexibility of hardened | cured material to be insufficient, thermal shock resistance to be inferior, and also moisture-heat resistance and adhesiveness to fall. (C) When the compounding quantity of urethane (meth) acrylate is less than 80 mass parts, the cohesive force of the hardened | cured material which hardened the adhesive composition falls, and it exists in the tendency for wet heat resistance and adhesiveness to be inferior. (C) When the compounding quantity of urethane (meth) acrylate exceeds 200 mass parts, the softness | flexibility of hardened | cured material is insufficient and it exists in the tendency for a thermal shock resistance to be inferior. (D) When the blending amount of the monofunctional (meth) acrylate having only one (meth) acrylic group is less than 30 parts by mass, the pressure-sensitive adhesive composition becomes too hard and the thermal shock resistance tends to be inferior. (D) When the compounding quantity of monofunctional (meth) acrylate exceeds 150 mass parts, a crosslinking density will fall and it exists in the tendency which is inferior to adhesiveness, heat-and-moisture resistance, and thermal shock resistance. (E) When the blending amount of the hydroxyl group-containing (meth) acrylamide is less than 5 parts by mass, the moist heat resistance of the cured product tends to be inferior. (E) When the compounding quantity of hydroxyl group containing (meth) acrylamide exceeds 25 mass parts, Tg of a composition becomes high and it exists in the tendency to be inferior to a thermal shock resistance.

<Laminate>
In the laminate of the present invention, an uncured adhesive layer made of the above-mentioned pressure-sensitive adhesive composition is laminated on one surface of a transparent substrate, and a substrate can be further laminated on the adhesive layer. Moreover, the adhesive layer may be hardened | cured in the laminated body by which the adhesion layer and the base material are laminated | stacked on the transparent base material.

  The thickness of the adhesive layer of the laminate is usually 25 to 1,000 μm, preferably 50 to 900 μm, and more preferably 80 to 800 μm. When the film thickness exceeds 1,000 μm, the amount of the pressure-sensitive adhesive composition required is large and coating becomes difficult. On the other hand, if the film thickness is less than 25 μm, it is difficult to make the film thickness uniform, which is not preferable.

<Base material>
As the transparent substrate on which the pressure-sensitive adhesive composition is applied, a substrate having a total light transmittance of 70% or more can be used. Transparent substrates include, for example, polyester films such as polyethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, cellulose films such as triacetyl cellulose, polyurethane films, polyurethane acrylate films, polyethylene films, polypropylene films, polyvinyl chloride films, poly Plastic films such as vinylidene chloride film, polyvinyl alcohol film, ethylene-vinyl acetate copolymer film, polystyrene film, polycarbonate film, acrylic resin film, norbornene resin film, cycloolefin resin film, and liquid crystal polymer film can be used.

  Moreover, as a base material laminated | stacked on an adhesion layer, the opaque base material whose total light transmittance is less than 70% other than the said transparent base material can also be used. For example, paper such as high-quality paper and glassine paper, metal foil of aluminum, copper, iron, woven fabric and nonwoven fabric made of glass fiber, natural fiber, synthetic fiber, etc. can be used.

  Functional layers such as a release treatment layer, an easy adhesion layer, a hard coat layer, an antireflection layer, a transparent conductive layer, and an electromagnetic wave shielding layer are provided on one side or both sides of these transparent or opaque substrates. Also good.

  The thickness of the transparent substrate and the substrate is preferably 10 to 500 μm. When the thickness of the substrate is thinner than 10 μm or thicker than 500 μm, the handleability at the time of use is lowered, which is not preferable.

<Formation of laminate>
The laminate is (1) a step of applying an adhesive composition to one side of a transparent substrate to form an adhesive layer, (2) a step of laminating a substrate on the adhesive layer, and (3) an adhesive. Of the steps of curing the layer, only (1) is produced by performing (1) and (2), or (1) to (3). In addition, when performing the process of (1) to (3), the order of the process of (2) and (3) may be reversed. That is, the adhesive layer may be cured after the base material is laminated on the uncured adhesive layer, or the base material may be laminated after the adhesive layer is cured.

  The application method of the pressure-sensitive adhesive composition is not particularly limited, and known application methods such as a roll coating method, a reverse coating method, a blade coating method, a bar coating method, a knife coating method, a die coating method, and a gravure coating method can be employed.

  Moreover, the hardening method in particular of the adhesion layer which consists of an adhesive composition is not restrict | limited, It can harden | cure with a heat | fever, an ultraviolet-ray (UV), and an electron beam (EB).

  Next, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited to this. The components used in the examples and comparative examples are as follows.

Ａ−５：下記式１８の多官能チオール化合物

Ａ−６：下記式１９の多官能チオール化合物

Ａ−７：下記式２０の多官能チオール化合物

Ａ−８：下記式２１の多官能チオール化合物

Ａ−９：下記式２２の多官能チオール化合物

Ａ’−１：１−オクタンチオール
＜（Ｂ）成分＞
Ｂ−１：ジメチロール−トリシクロデカンジアクリレート
Ｂ−２：ジペンタエリスリトールヘキサアクリレート
Ｂ−３：エトキシ化イソシアヌル酸トリアクリレート
Ｂ−４：ビスフェノールＡのＥＯ付加物ジメタクリレート
Ｂ−５：トリメチロールプロパントリメタクリレート
Ｂ−６：１，６−ヘキサンジオールジメタクリレート
＜（Ｄ）成分＞
Ｄ−１：２−エチルヘキシルアクリレート
Ｄ−２：イソボニルアクリレート
Ｄ−３：２−ヒドロキシエチルアクリレート
Ｄ−４：４−ヒドロキシブチルアクリレート
Ｄ−５：テトラヒドロフルフリルアクリレート
＜（Ｅ）成分＞
Ｅ−１：Ｎ−(２−ヒドロキシメチル)アクリルアミド
Ｅ−２：Ｎ−(２−ヒドロキシエチル)アクリルアミド
Ｅ−３：Ｎ−(２−ヒドロキシプロピル)アクリルアミド
Ｅ’−１：ジメチルアクリルアミド
Ｅ’−２：アクリルロイルアクリルアミド <(A) component>
A-1: Trimethylolpropane tris (3-mercaptopropionate)
A-2: Dipentaerythritol hexakis (3-mercaptopropionate)
A-3: Tris-[(3-mercaptopropionyloxy) -ethyl] -isocyanurate A-4: Polyfunctional thiol compound of the following formula 17

A-5: Polyfunctional thiol compound of the following formula 18

A-6: Polyfunctional thiol compound of the following formula 19

A-7: Polyfunctional thiol compound of the following formula 20

A-8: Polyfunctional thiol compound of the following formula 21

A-9: Polyfunctional thiol compound of the following formula 22

A′-1: 1-octanethiol <(B) component>
B-1: dimethylol-tricyclodecane diacrylate B-2: dipentaerythritol hexaacrylate B-3: ethoxylated isocyanuric acid triacrylate B-4: EO adduct of bisphenol A dimethacrylate B-5: trimethylolpropane tri Methacrylate B-6: 1,6-hexanediol dimethacrylate <(D) component>
D-1: 2-ethylhexyl acrylate D-2: isobornyl acrylate D-3: 2-hydroxyethyl acrylate D-4: 4-hydroxybutyl acrylate D-5: tetrahydrofurfuryl acrylate <(E) component>
E-1: N- (2-hydroxymethyl) acrylamide E-2: N- (2-hydroxyethyl) acrylamide E-3: N- (2-hydroxypropyl) acrylamide E′-1: Dimethylacrylamide E′-2 : Acrylic Roylacrylamide

<Production of component (C)>
(Production of Diol Compound (c-1))
A reaction vessel equipped with a stirrer, a rectifying column, a nitrogen inlet tube, and a thermometer was charged with 150.2 parts by mass of adipic acid and 161.3 parts by mass of 3-methyl-1,5-pentanediol, and 140 in a nitrogen atmosphere. Heated and stirred to ° C. This was charged with 0.01 parts by mass of tetrabutyl titanate, and the temperature was raised to 220 ° C. to perform a dehydration reaction. Then, it hold | maintained at 220 degreeC continuously and dehydration reaction was performed. After 18 hours from the start of the dehydration reaction, the contents were cooled to obtain a diol compound (c-1) (weight average molecular weight: 1600).

(Production of diol compound (c-2))
A reaction vessel equipped with a stirrer, a rectifying column, a nitrogen introduction tube, and a thermometer was charged with 158.5 parts by mass of pimelic acid and 202.1 parts by mass of 3-methyl-1,5-pentanediol, and 140 in a nitrogen atmosphere. Heated and stirred to ° C. This was charged with 0.01 parts by mass of tetrabutyl titanate, and the temperature was raised to 220 ° C. to perform a dehydration reaction. Then, it hold | maintained at 220 degreeC continuously and performed dehydration reaction. After 18 hours from the start of the dehydration reaction, the contents were cooled to obtain a diol compound (c-2) (weight average molecular weight: 1750).

(Manufacture of urethane (meth) acrylate)
In a reaction vessel equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, 160.3 parts by mass of the diol compound (c-1) was charged, and stirring was started. Next, 0.1 parts by weight of dibutyltin laurate and 77.4 parts by weight of 1,6-diisocyanate-2,2,4-trimethylhexane were added as diisocyanate, and the internal temperature was raised to 80 ° C. while paying attention to heat generation. Then, the mixture was stirred for 3 hours while maintaining the temperature. Furthermore, 0.1 part by mass of methoquinone as a polymerization inhibitor and 31.2 parts by mass of propylene glycol monoacrylate as an acrylate were added and stirred at 85 ° C. for 2 hours to obtain urethane (meth) acrylate (C-1). Obtained (weight average molecular weight: 9500).

Urethane (meth) acrylates (C-2) to (C-5) were obtained in the same manner as described above except that the diol compounds, diisocyanates, and acrylates shown in Table 1 below were used.

<Manufacture of an adhesive composition>
Each component was added to the stirring vessel as shown in Tables 2 to 5 below, mixed and stirred for 2 hours, and Examples 1-1 to 1-22, 2-1 to 2-43, and Comparative Examples 1-1 to 1 were used. A pressure-sensitive adhesive composition of -11 was obtained.

<Manufacture of laminates>
<Manufacture of laminated body 1>
On the transparent substrate (PET, thickness: 100 μm, total light transmittance: 91%, manufactured by Toyobo Co., Ltd. (product number: A4100)), the pressure-sensitive adhesive composition of each Example and Comparative Example is formed to a thickness of 500 μm using a die coater. Then, a base material (PC, thickness: 125 μm, total light transmittance: 90%, manufactured by Escarbo sheet (product number C000)) was placed on the formed adhesive layer and laminated. Then, ultraviolet irradiation (700 mJ / cm ² ) was performed using a metal halide lamp to cure the adhesive layer, and Examples 1-1 to 1-22, 2-1 to 2-43 and Comparative Examples 1-1 to 1- 11 laminates 1 were obtained.

<Manufacture of laminated body 2>
On the transparent substrate (PC, thickness: 125 μm, total light transmittance: 90%, made of Escarbo sheet (product number C000)), the pressure-sensitive adhesive composition of each Example and Comparative Example was formed with a die coater to a film thickness of 500 μm. The base material (glass, thickness: 0.7 mm, total light transmittance: 91%, manufactured by Corning (product number: EAGLE XG)) was placed on the formed adhesive layer and laminated. . Then, ultraviolet irradiation (700 mJ / cm ² ) was performed using a metal halide lamp to cure the adhesive layer, and Examples 1-1 to 1-22, 2-1 to 2-43 and Comparative Examples 1-1 to 1- 11 laminates 2 were obtained.

<Evaluation method>
The properties of the pressure-sensitive adhesive compositions and laminates obtained in each Example and Comparative Example were evaluated by the methods described below. The evaluation results are shown in Tables 2 to 5 above.

-Adhesion Using a desktop material testing machine (STA-1150 manufactured by Orientec Co., Ltd.), the adhesion of the laminates 1 of each Example and Comparative Example was measured according to JISZ0237: 2009 (peeling speed: 300 mm / min). 180 degree peel force test).
○: 15 N / 20 mm or more ×: less than 15 N / 20 mm

・ Heat and heat resistance 1 (durability)
The laminated body 1 of each Example and the comparative example was cut | judged to the magnitude | size of 50 mm length and width 50mm, and the haze value of the obtained sample was measured with the haze meter (Nippon Denshoku Industries NDH2000). After the measurement, the sample was allowed to stand for 1000 hours in a constant temperature and humidity tester at 60 ° C. and 95% RH. Thereafter, the sample was taken out from the constant temperature and humidity tester and allowed to stand at 23 ° C. and 50% RH for 30 minutes, and then the appearance of the sample was visually observed, and the haze value was measured with a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.). Measured with
○: No change in haze value before and after treatment with a constant temperature and humidity tester without any abnormality such as peeling on the appearance of the sample or dripping of the pressure sensitive adhesive composition (haze value before treatment-haze after treatment) Value) is less than ± 3%.
X: There are abnormalities such as peeling, foaming, and dripping of the pressure-sensitive adhesive composition on the appearance of the sample. Or the change value of the haze value before and after the treatment in the constant temperature and humidity tester (the haze value before the treatment−the haze value after the treatment) is ± 3% or more.

・ Heat and heat resistance 2 (durability)
The laminated body 1 of each Example and the comparative example was cut | judged to the magnitude | size of 50 mm length and width 50mm, and the haze value of the obtained sample was measured with the haze meter (Nippon Denshoku Industries NDH2000). After the measurement, the sample was allowed to stand for 2000 hours in a constant temperature and humidity tester at 85 ° C. and 85% RH. Thereafter, the sample was taken out from the constant temperature and humidity tester and allowed to stand at 23 ° C. and 50% RH for 30 minutes, and then the appearance of the sample was visually observed, and the haze value was measured with a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.). Measured at
○: No change in haze value before and after treatment with a constant temperature and humidity tester without any abnormality such as peeling on the appearance of the sample or dripping of the pressure sensitive adhesive composition (haze value before treatment-haze after treatment) Value) is less than ± 3%.
X: There are abnormalities such as peeling, foaming, and dripping of the pressure-sensitive adhesive composition on the appearance of the sample. Or the change value of the haze value before and after the treatment in the constant temperature and humidity tester (the haze value before the treatment−the haze value after the treatment) is ± 3% or more.

-Thermal shock resistance (flexibility)
The laminated body 1 and the laminated body 2 of each Example and the comparative example were cut | judged to the magnitude | size of 150 mm length and 200 mm in width, and the haze value of the obtained sample was measured with the haze meter (Nippon Denshoku Industries NDH2000). After the measurement, the sample was processed for 300 cycles with a thermal shock tester under the following test conditions.
-High-temperature side test conditions: 95 ° C, 30 minutes-Low-temperature side test conditions: -40 ° C, 30 minutes Then, the sample was taken out of the thermal shock tester and left at 23 ° C, 50% RH for 30 minutes, then the sample The haze value was measured with a haze meter (NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.).
A: In the laminated body 1 and the laminated body 2, there is no abnormality such as peeling of the sample appearance or dripping of the pressure-sensitive adhesive composition, and the change in the haze value before and after the treatment in the constant temperature and humidity tester (treatment) The previous haze value−the haze value after the treatment) is less than ± 3%.
◯: There are abnormalities such as peeling, foaming, and dripping of the pressure-sensitive adhesive composition in the laminate 2 on the appearance of the sample. In addition, there is no abnormality such as peeling of the sample in the laminate 1 or dripping of the pressure-sensitive adhesive composition, and the change in the haze value before and after the treatment in the constant temperature and humidity tester (the haze value before the treatment) -Haze value after treatment) is less than ± 3%.
X: In the laminated body 1 and the laminated body 2, there are abnormalities such as peeling off the appearance of the sample, foaming, and dripping of the pressure-sensitive adhesive composition. Or the change value of the haze value before and after the treatment in the constant temperature and humidity tester (the haze value before the treatment−the haze value after the treatment) is ± 3% or more.

-Storage stability Immediately after mixing the pressure-sensitive adhesive compositions of each Example and Comparative Example, the viscosity at 25 ° C (viscosity immediately after mixing) was measured, and after heating at 50 ° C for 60 days, the viscosity (viscosity after heating) was measured again. ) Was measured, the viscosity after heating was divided by the viscosity immediately after mixing, and the rate of thickening was calculated and evaluated as follows. The viscosity was measured under the following conditions using an R-type viscometer RE-85U manufactured by Toki Sangyo Co., Ltd.
Rotor used: 1 ° 34 '× R24
Measurement range: 0.5183 to 103.7 Pa · s
A: Thickening rate is less than 1.02 B: Thickening rate is 1.02 or more, less than 1.50 X: Thickening rate is 1.50 or more

As a result of the above tests, the pressure-sensitive adhesive composition of each example had excellent adhesion, wet heat resistance (durability), thermal shock resistance (flexibility), and storage stability. On the other hand, since Comparative Example 1-1 had too little (B) component, the heat-and-moisture resistance was inferior. Since comparative example 1-2 had too much (B) component, adhesiveness, heat-and-moisture resistance, and thermal shock resistance were inferior. Since Comparative Example 1-3 had too little (C) component, adhesiveness and heat-and-moisture resistance were inferior. Since Comparative Example 1-4 has too much (C) component, the thermal shock resistance was inferior. In Comparative Example 1-5, since the amount of the component (D) was too small, the thermal shock resistance was inferior. Since Comparative Example 1-6 has too much (D) component, adhesiveness, heat-and-moisture resistance, and thermal shock resistance were inferior. Since Comparative Example 1-7 had too little (E) component, the heat-and-moisture resistance was inferior. Since Comparative Example 1-8 contained too much (E) component, the heat-and-moisture resistance and the thermal shock resistance were inferior. In Comparative Examples 1-9 and 1-10, since the component (E) did not have a hydroxyl group, the heat and moisture resistance was inferior. Since Comparative Example 1-11 (A) component has only one thiol group, adhesiveness, heat-and-moisture resistance, and thermal shock resistance were inferior.

Claims (7)

(A) a polyfunctional thiol compound having 2 to 6 thiol groups;
(B) a polyfunctional (meth) acrylate having 2 to 6 (meth) acryl groups;
(C) urethane (meth) acrylate having a weight average molecular weight of 1000 to 15000 represented by the following formula 1,
(D) a monofunctional (meth) acrylate having only one (meth) acryl group;
(E) A pressure-sensitive adhesive composition containing hydroxyl group-containing (meth) acrylamide,
(A) When the polyfunctional thiol compound having 2 to 6 thiol groups is taken as 100 parts by mass,
(B) Polyfunctional (meth) acrylate: 5 to 25 parts by mass (C) Urethane (meth) acrylate: 80 to 200 parts by mass (D) Monofunctional (meth) acrylate: 30 to 150 parts by mass (E) Hydroxyl group-containing (Meth) acrylamide: A pressure-sensitive adhesive composition containing 5 to 25 parts by mass.

(In the formula, a is an integer of ¹ to 15. R ¹ is a hydrocarbon group having 1 to 14 carbon atoms, R ² is a hydrocarbon group having 1 to 14 carbon atoms, and poly represented by the following formula 2. An ether group or a polyester group represented by the following formula 3, R ³ is a hydrogen atom or a methyl group, and R ⁴ is a hydrocarbon group having 1 to 14 carbon atoms.)

(In the formula, b is an integer of 1 to 20. R ⁵ is an independent hydrocarbon group having 2 to 14 carbon atoms.)

(In the formula, c is an integer of 1 to 20. R ⁶ and R ⁷ are each a hydrocarbon group having 1 to 14 carbon atoms, which may be the same or different.) The pressure-sensitive adhesive composition according to claim 1, wherein the polyfunctional thiol compound having 2 to 6 (A) thiol groups is a polyfunctional thiol compound represented by the following formula 4.

(In the formula, d is 2 or 3, e is 0 or 1, f is 1 or 2, and the sum of d, e, and f is 4. R ⁸ is a methylene group, an ethylene group, or It is an isopropylene group, R ⁹ is a divalent functional group represented by the following formula 5 or 6, R ¹⁰ is a methyl group or an ethyl group, and R ¹¹ has 1 to 12 carbon atoms. Hydrocarbon group.)

(In the formula, R ¹² is a hydrogen atom or a methyl group.)

(In the formula, R ¹³ is a hydrogen atom or a methyl group.) The pressure-sensitive adhesive composition according to claim 1, wherein the polyfunctional thiol compound having 2 to 6 (A) thiol groups is a polyfunctional thiol compound represented by the following formula 7.

(In the formula, g is an integer of 2 to 5, h is an integer of 0 to 2, i is an integer of 1 to 4, and the sum of g, h, and i is 6. R ¹⁴ is the following. It is a hexavalent functional group represented by Formula 8, R ¹⁵ is a methylene group, ethylene group or isopropylene group, and R ¹⁶ is a divalent functional group represented by Formula 5 or Formula 6 below. Yes, R ¹⁷ is a methyl group or an ethyl group, and R ¹⁸ is a hydrocarbon group having 1 to 12 carbon atoms.)

(In the formula, R ¹² is a hydrogen atom or a methyl group.)

(In the formula, R ¹³ is a hydrogen atom or a methyl group.)

The pressure-sensitive adhesive composition according to claim 1, wherein the polyfunctional thiol compound having 2 to 6 (A) thiol groups is a polyfunctional thiol compound represented by the following formula 9.

(In the formula, R ¹⁹ is a trivalent functional group represented by the following formula 10, R ²⁰ is a divalent functional group represented by the following formula 5 or 6, and R ²¹ has 1 carbon atom. ˜12 hydrocarbon groups.)

(In the formula, R ²² is a methylene group, an ethylene group or an isopropylene group.)

(In the formula, R ¹² is a hydrogen atom or a methyl group.)

(In the formula, R ¹³ is a hydrogen atom or a methyl group.)   The laminated body by which the uncured adhesive layer which consists of an adhesive composition in any one of Claims 1 thru | or 4 is laminated | stacked on one surface of the transparent base material.   The laminated body by which the uncured adhesive layer and base material which consist of an adhesive composition in any one of Claims 1 thru | or 4 are laminated | stacked in this order on one surface of the transparent base material. The laminated body by which the adhesion layer and base material which the adhesive composition in any one of Claims 1 thru | or 4 hardened | cured are laminated | stacked in this order on one surface of the transparent base material.