TW201934709A - Resin composition, resin layer, and layered sheet - Google Patents

Abstract

Provided are a resin layer capable of strongly adhering to a rough surface and to a plastic, the resin layer having high holding power and exhibiting good adhesion even at low temperature, a resin composition suitable for forming the resin layer, and a layered sheet including the resin layer. The resin composition provided by the present invention contains a (meth)acrylic polymer having a Tg of -40 DEG C or below, and 5-40 parts by weight of a tackifying resin with respect to 100 parts by weight of the (meth)acrylic polymer. The (meth)acrylic polymer is a polymer of monomer components including: 50-97 wt% of an alkyl (meth)acrylate (A1) having a C8-18 branched alkyl group at a terminal end of an ester group, a homopolymer of the alkyl (meth)acrylate (A1) having a Tg of -50 DEG C or below; and 3-50 wt% of a (meth)acrylate (A2) having an ether bond in the molecular skeleton thereof, a homopolymer of the (meth)acrylate (A2) having a Tg of -40 DEG C or below.

Description

Resin composition, resin layer and laminated sheet

The present invention relates to a resin composition, a resin layer, and a laminated sheet. This application claims priority based on Japanese Patent Application No. 2017-254900 filed on December 28, 2017 and Japanese Patent Application No. 2018-194150 filed on October 15, 2018. The entire contents of the application Is incorporated herein by reference.

Generally, an adhesive (also referred to as a pressure-sensitive adhesive. The same applies hereinafter) has a state of being a soft solid (viscoelastic body) in a temperature region near room temperature, and is bonded to an adherend by pressure. Taking advantage of this property effectively, the adhesive is in the form of an adhesive sheet (laminated sheet) having a laminated structure of a resin layer that can function as an adhesive on one or both sides of a support, and is widely used in home appliances to automobiles , OA (Office Automation, Office Automation) equipment and other industrial fields. As technical documents related to an adhesive agent or an adhesive sheet, patent documents 1 and 2 are mentioned.
[Prior technical literature]
[Patent Literature]

Patent Document 1: Japanese Patent Application Publication No. Hei 08-104847 Patent Document 2: International Publication No. 2013/099683

[Problems to be solved by the invention]

Previous laminated sheets with adhesives have rough surfaces (such as those with convex and concave shapes) such as concrete, mortar, gypsum board, coniferous board, wood cement board, calcium silicate board, tile and fiber reinforced cement board, etc. Surfaces), or plastic adherends such as polypropylene, which are generally recognized as low-polarity adherends, have a high degree of difficulty in adhering, and the adhesion force tends to be insufficient. Therefore, in many cases, an adhesive is used instead of an adhesive for these adherends having a rough surface. In addition, when an adhesive is applied to a low-polar adherend, in many cases, it is generally necessary to take measures such as a primer coating treatment. However, in recent years, as the need to more easily bond the adherends having a rough surface to each other, or to attach and fix various other adherends including a low-polar adherend, the use of adhesion is strongly desired. It is not necessary to use a primer or the like to laminate a sheet such as a sheet to join an adherend having a rough surface or a low-polar adherend.

A laminated sheet such as an adhesive sheet can be used for the purpose of joining an adherend or a plastic member having a rough surface as described above. From the viewpoint of keeping the weight fixed to the adherend in the fixed state for a long period of time, it is also necessary to hold the laminated sheet such as an adhesive sheet used for an adherend having a rough surface or a plastic member. Furthermore, the bonding operation of the adherend having a rough surface can also be performed in a low-temperature environment such as outdoor in winter. Therefore, it is preferable that a laminated sheet such as an adhesive sheet shows a good rough surface even at a low temperature. Then sex.

Therefore, an object of the present invention is to provide a holding force that can be strongly adhered to a generally adherent body such as glass, stainless steel, aluminum, or the like, and firmly adhered to any of a rough surface and a plastic. A resin layer that is high and exhibits good adhesion even at low temperatures; and a resin composition suitable for the formation of the resin layer. A related other object is to provide a laminated sheet including the above resin layer.
[Technical means to solve the problem]

According to the specification, there is provided a resin composition containing a (meth) acrylic polymer having a glass transition temperature (Tg) of -40 ° C or lower, and 5 parts by weight based on 100 parts by weight of the (meth) acrylic polymer. The adhesion-imparting resin is at least 40 parts by weight. The (meth) acrylic polymer is an alkyl (meth) acrylate (A1) containing a homopolymer having a Tg of -50 ° C or lower and having a branched alkyl group having 8 to 18 carbons at the end of the ester group. And a polymer of a monomer component of (meth) acrylate (A2) having a Tg of homopolymer of -40 ° C or lower and having an ether bond in a molecular skeleton. The said monomer component contains the said (meth) acrylic acid alkyl ester (A1) in the ratio of 50-97 weight%, and contains the said (meth) acrylic acid ester (A2) which has an ether bond in the ratio of 3-50 weight%. .

In addition, below, the said (meth) acrylic-acid alkylester (A1) may be described as "monomer A1." Moreover, the (meth) acrylate (A2) which has the said ether bond may be described as "monomer A2."

According to the resin composition having the above-mentioned configuration, by including a specific amount of the adhesion-imparting resin to the (meth) acrylic polymer, the adhesion to the adherend can be improved. In addition, since the (meth) acrylic polymer is a polymer containing monomer components of the monomers A1 and A2 at a specific ratio, it is easy to form a rough surface having a high holding force and exhibiting good roughness even at low temperatures. Surface-adhesive resin layer. Therefore, by using the above-mentioned (meth) acrylic polymer in combination with the above-mentioned specific amount of adhesion-imparting resin, it is possible to simultaneously achieve a higher adhesion force and a higher retention force to rough surfaces or plastics, and Adhesion at low temperature.

In some aspects of the resin composition, the total ratio of the monomer A1 and the monomer A2 may be 75% by weight or more of all monomer components forming the (meth) acrylic polymer. The resin composition disclosed herein can be preferably implemented using a (meth) acrylic polymer as a polymer of a monomer component having such a composition.

As the monomer A2, the general formula (1) can be preferably used:
CH ₂ = CR ¹ -COO- (AO) _n -R ² ;
The indicated monomer. Here, in the general formula (1), R ¹ is a hydrogen atom or a methyl group. AO is an alkoxy group having 2 to 3 carbon atoms. n represents the number of the average addition mole number of the said alkoxy group, and it can be 1-10, for example. R ² is an aromatic ring, or a linear, branched, or alicyclic alkyl group. According to the monomer A2 having such a structure, it is easy to form a resin layer that is excellent in adhesion even at low temperatures, and achieves a good balance of adhesion and holding force by a moderate cohesiveness.

In some aspects, the adhesion-imparting resin may include at least one selected from the group consisting of a rosin-based adhesion-imparting resin, a terpene-based adhesion-imparting resin, a petroleum-based adhesion-imparting resin, and a styrene-based adhesion-imparting resin. The techniques disclosed herein can be better implemented using such adhesion-imparting resins.

The resin composition disclosed herein may include at least one adhesion-imparting resin having a softening point of 90 ° C or higher and 160 ° C. By using an adhesion-imparting resin having a softening point in the above range, a resin having a good balance between adhesiveness and cohesiveness at a room temperature range and a good adhesion to a rough surface even at a low temperature range is formed. Layer of tendencies.

The monomer component constituting the (meth) acrylic polymer may include at least one functional group-containing monomer selected from the group consisting of a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group. body. Such a functional group-containing monomer can help adjust the cohesiveness of the resin layer or the adjustment of the storage elastic modulus G ′.

The weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 350,000 or more. According to the (meth) acrylic polymer having such Mw, it is easy to obtain a resin layer having a good balance and simultaneously achieving adhesion and cohesiveness to rough surfaces and plastic members.

A crosslinking agent may be contained in the resin composition. The cross-linking agent can help adjust the cohesiveness of the resin layer or the storage elastic modulus G ′. In some aspects, content of the said crosslinking agent may be 0.01 weight part or more and 5 weight part or less with respect to 100 weight part of said (meth) acrylic-type polymers. As the crosslinking agent, one or both of an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent can be preferably used.

According to the specification, a resin layer formed from any of the resin compositions disclosed herein is provided. Such a resin layer can exhibit good adhesion to adherends such as rough surfaces, plastics, etc., and has a high holding force by having moderate cohesiveness, and exhibits good adhesion even in a low temperature range.

In some aspects, the storage elastic modulus G 'of the resin layer at 23 ° C may be 1.0 × 10 ⁴ Pa or more and 5.0 × 10 ⁴ Pa or less, and the storage elastic modulus G ′ at -10 ° C may be 3.0 × 10 ⁴ Pa or more and 7.0 × 10 ⁵ Pa or less. A resin layer having such characteristics is preferred because it has a good balance between the adhesion force and the holding force in the room temperature range, and also exhibits a good adhesion tendency even in the low temperature range.

In addition, hereinafter, the storage elastic modulus G 'at 23 ° C is sometimes referred to as "storage elastic modulus G' (23 ° C)". Similarly, the storage elastic modulus G 'at -10 ° C may be described as "storage elastic modulus G' (-10 ° C)".

In some aspects, the polymer gel fraction of the resin layer may be in a range of 20% by weight to 95% by weight. According to the resin layer in which the polymer gel fraction is in the above range, it is easy and preferable to simultaneously achieve adhesion to a rough surface (for example, adhesion at low temperature) and cohesiveness.

According to the specification, there is provided a laminated sheet having any of the resin layers disclosed herein on at least one side of a support. Such a laminated sheet can be used, for example, in a state where the resin layer is attached to an adherend, and is preferably used for bonding or fixing the adherend. Non-limiting examples of the above-mentioned adherend include the adherend having a rough surface as described above or various plastic materials. As the support, for example, a constitution including at least any one of a plastic film, paper, non-woven fabric, and a sheet containing air bubbles or particles can be preferably used.

In some aspects, the 180 ° peeling adhesion force of the above resin layer measured at an environment of 23 ° C. and a peeling speed of 300 mm / min may be 10 N / 20 mm or more. Hereinafter, the 180 ° peeling adhesive force at 23 ° C may be described as “room temperature adhesive force”. According to the technology disclosed herein, the above-mentioned room temperature adhesion can be achieved better by using the above-mentioned (meth) acrylic polymer in combination with a specific amount of adhesion-imparting resin.

In some aspects, the 180 ° peeling adhesion force of the resin layer measured at an environment of -10 ° C and a peeling speed of 300 mm / min may be 5 N / 20 mm or more. Hereinafter, the 180 ° peeling adhesive force at -10 ° C may be described as "low temperature adhesive force". Since the (meth) acrylic polymer is a polymer containing monomer components of the monomer A1 and the monomer A2 at a specific ratio, it is excellent in flexibility even in a low temperature range. Therefore, according to the technology disclosed here, the above-mentioned low temperature adhesive force can be preferably achieved by using the (meth) acrylic polymer in combination with a specific amount of adhesion-imparting resin.

The resin composition, the resin layer, and the laminated sheet disclosed herein can be used as, for example, an adhesive composition, an adhesive layer, and an adhesive sheet.

Furthermore, a proper combination of the above elements may also be included in the scope of the invention claimed by the patent application.

Hereinafter, preferred embodiments of the present invention will be described. Based on the teachings on the implementation of the invention described in this specification and the technical common sense at the time of application, practitioners can understand things other than those specifically mentioned in this specification and what is needed to implement the invention. The present invention can be implemented based on the contents disclosed in this specification and technical common sense in the field.
Furthermore, in the drawings below, the same symbols are used to describe components and parts that perform the same function, and repeated descriptions may be omitted or simplified. In addition, the embodiments described in the drawings are modeled in order to clearly explain the present invention, and do not necessarily accurately represent the size or reduction ratio of the product actually provided.

In addition, in this specification, "(meth) acrylate" means the meaning of acrylate and methacrylate. Similarly, in this specification, "(meth) acrylic acid" refers to the meaning of acrylic acid and methacrylic acid, and "(meth) acrylfluorene" refers to the meaning of acrylic acid and methacrylic acid. The meaning of base.

The resin composition disclosed herein is a polymer containing monomer components of 50 to 97% by weight of monomer A1 and 3 to 50% by weight of monomer A2, and (meth) acrylic based on a Tg of -40 ° C or lower. The polymer and the adhesion-imparting resin are 5 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the (meth) acrylic polymer.
The (meth) acrylic polymer is obtained by adding a specific amount of (meth) acrylic acid alkyl ester (monomer A1) containing a branched alkyl group having 8 to 18 carbon atoms, and (Meth) acrylic acid ester (monomer A2) is obtained by polymerizing a specific amount of a monomer component. Moreover, the Tg of the homopolymer of each of the monomers A1 and A2 was low, and the (meth) acrylic polymer obtained also had a low Tg. According to the resin composition containing such a (meth) acrylic polymer, by the action of the monomer A1 and the monomer A2, it is possible to exhibit a higher adhesion force and a higher retention force to an adherend having a rough surface. .

Monomer A1 has low Tg and moderate cohesion and adhesion. Monomer A2 has low Tg and moderate polarity, and has a better interaction with the surface of the adherend. As a result, it is estimated that the resin composition containing the above (meth) acrylic polymer has moderate softness and cohesion, and interaction with the interface, and can exhibit higher adhesion force and better adhesion to the adherend having a rough surface. High retention.

In addition, the resin composition disclosed herein can improve the wettability of the low-polar adherend and the interface with the adherend by including an adhesion-imparting resin, and by improving the elastic modulus of the adhesive block. It can impart moderate cohesion to the resin layer. Thereby, it is possible to show a high adhesion force to various adherends such as rough surfaces or plastics. In a low-polarity adherend such as a polyolefin resin, it is particularly effective to use an adhesion-imparting resin. In addition, it is estimated that by using a specific amount of the adhesion-imparting resin in combination with the (meth) acrylic polymer described above, it is possible to have an effect by using an adhesion-imparting resin and suppress a decrease in adhesiveness at low temperatures. .

＜ monomer A1 ＞
As the monomer A1, an alkyl (meth) acrylate having a Tg of a homopolymer of -50 ° C or lower and a branched alkyl group having 8 to 18 carbon atoms at the end of the ester group is used. From the viewpoint of improving the adhesion to an adherend having a rough surface, the Tg of the homopolymer of the monomer A1 is preferably -55 ° C or lower, more preferably -60 ° C or lower. From the viewpoint of improving the retention, the Tg of the homopolymer of the monomer A1 is preferably -80 ° C or higher, and more preferably -75 ° C or higher. From the viewpoint of imparting moderate flexibility to the resin layer and from the viewpoint of improving the cohesiveness of the resin layer, the number of carbon atoms in the alkyl group of the monomer A1 is preferably from 8 to 16, and more preferably from 8 to 14.

In the technology disclosed herein, the Tg of the homopolymer of each monomer is the value described in the "Polymer Handbook" (3rd edition, John Wiley & Sons, Inc., 1989). When a plurality of values are described in the polymer manual, conventional values are used. For the monomers not listed in the above polymer manual, the catalog values of the monomer manufacturing companies are used.

As the Tg of the homopolymer of the monomer which is not described in the polymer manual and does not provide the catalog value of the monomer manufacturing company, the value obtained by the following measurement method is used. That is, in a reactor equipped with a thermometer, a stirrer, a nitrogen introduction pipe, and a reflux cooling pipe, 100 parts by weight of the monomer to be measured, 0.1 part by weight of 2,2'-azobisisobutyronitrile, and a polymerization solvent were charged. 200 parts by weight of ethyl acetate was stirred for 1 hour while introducing nitrogen gas. After the oxygen in the polymerization system was removed in this way, the temperature was raised to 60 ° C and the reaction was performed for 12 hours. Then, it cooled to room temperature, cast this homopolymer solution on the release liner, and dried it, and produced the test sample (sheet-like homopolymer) with a thickness of about 50 micrometers. A sample of 2 to 3 mg was collected from the obtained test sample, put into an aluminum container, and rolled to perform DSC (differential scanning calorimetry) measurement (Q-2000 manufactured by TA Instruments). The temperature control program was set to -80 ° C to 150 ° C (measurement speed: 10 ° C / min), and the measurement was performed under a nitrogen (50 ml / min) atmosphere. The value of Tmg (midpoint glass transition temperature) was read from the obtained graph, and this value was set to the Tg of the homopolymer.

Examples of the monomer A1 include 2-ethylhexyl acrylate (carbon number 8, Tg of homopolymer = -70 ° C), isooctyl acrylate (carbon number 8, Tg of homopolymer = -58 ° C) ), Isononyl acrylate (carbon number 9, Tg of homopolymer = -58 ° C), isodecyl acrylate (carbon number 10, Tg of homopolymer = -60 ° C), isomyristyl acrylate (carbon number 14, Tg = -56 ° C), isoundecyl acrylate, isododecyl acrylate, isopentadecyl acrylate, isohexadecyl acrylate, isoheptadecyl acrylate, acrylic acid Isooctadecyl ester, and the methacrylate ester exemplified above. The monomer A1 may be used singly or in combination of two or more kinds. In addition, from the viewpoint of improving the adhesive force of the resin layer or the viewpoint of polymerization reactivity, the monomer A1 is preferably an alkyl acrylate.

＜ monomer A2 ＞
As the monomer A2, a (meth) acrylate having a Tg of a homopolymer of -40 ° C or lower and having an ether bond in a molecular skeleton is used. From the viewpoint of improving the adhesion to an adherend having a rough surface, the Tg of the homopolymer of the monomer A2 is preferably -45 ° C or lower, more preferably -50 ° C or lower. From the viewpoint of improving the adhesion and holding power of an adherend having a rough surface, the Tg of the homopolymer of the monomer A2 is preferably -90 ° C or higher, more preferably -80 ° C or higher. In addition, the above-mentioned ether bond in the molecular skeleton of the monomer A2 means a chain ether bond, which is different from a cyclic ether bond such as an epoxy group or an oxetanyl group.

As the monomer A2, an unsaturated double bond having a (meth) acrylfluorenyl group and a chain ether bond can be used without particular limitation. Examples of the monomer A2 include the general formula (1): CH ₂ = CR ¹ -COO- (AO) _n -R ² ; a monomer represented by the formula, and the like. Here, R ¹ in the general formula (1) is a hydrogen atom or a methyl group. AO is an alkoxy group having 2 to 3 carbon atoms. n is a number representing the average addition mole number of alkoxy groups. R ² is a monovalent organic group which does not contain an ether bond, and is preferably a hydrocarbon group. The monomer A2 may be used singly or in combination of two or more kinds.

In the general formula (1), n may be 1 to 10, for example. From the viewpoints of polarity rank and polymerization reactivity, in some aspects, n in the general formula (1) is preferably 2 to 8, more preferably 2 to 5.

R ² in the general formula (1) is preferably an unsubstituted aromatic ring, or a linear, branched, or alicyclic alkyl group. Examples of the aromatic ring of R ² include a phenyl group and the like. Examples of the linear alkyl group and branched alkyl group of R ² include isopropyl group, ethyl group, and methyl group. Examples of the alicyclic alkyl group of R ² include a cyclohexyl group and the like. In terms of a (meth) acrylic acid ester containing a chain ether bond having a low Tg which is easily a homopolymer, R ^{2 is} preferably a linear alkyl group or a branched alkyl group, and more preferably a linear alkyl group. . In addition, from the viewpoint of easily becoming a monomer A2 having a moderate polarity, the carbon number of R ² is preferably 1 to 6, more preferably 1 to 5, or 1 to 4 or 1 to 3.

Examples of the monomer represented by the general formula (1) include methoxy polyethylene glycol (meth) acrylate, ethoxy polyethylene glycol (meth) acrylate, and propoxy polyethylene glycol ( Meth) acrylate and other AO are alkoxyoxy monomers having 2 carbon atoms; and methoxy polypropylene glycol (meth) acrylate, ethoxy polypropylene glycol (meth) acrylate, and propoxy polypropylene glycol AO such as (meth) acrylate is a monomer having 3 alkoxy groups. From the viewpoint of polymerization reactivity, the monomer A2 in which R ¹ in the general formula (1) is a hydrogen atom is preferred. That is, the monomer A2 is preferably an acrylate.

From the viewpoint of having a moderate polarity balance, AO in the general formula (1) is preferably an alkoxy group having 2 carbon atoms, that is, an oxyethylene group. Specific compounds include ethyl carbitol acrylate (ethoxyethoxyethyl acrylate) (Tg of homopolymer = -67 ° C), and methoxytriethylene glycol acrylate (homopolymer Tg = -57 ° C) and so on.

In the technology disclosed herein, the amount of the monomer A1 is suitably 50 to 97% by weight of all the monomer components forming the (meth) acrylic polymer. From the viewpoint of improving the adhesion and holding power to the rough surface, the usage amount of the monomer A1 is preferably 55% by weight or more, more preferably 58% by weight or more, and still more preferably 59% by weight. the above. From the viewpoint of improving the adhesion and holding power to the rough surface, the use amount of the monomer A1 is preferably 95% by weight or less, more preferably 93% by weight or less, and still more preferably 91% by weight. % By weight or less.

In the technology disclosed herein, the amount of the monomer A2 is suitably 3 to 50% by weight of all the monomer components forming the (meth) acrylic polymer. From the viewpoint of improving the adhesion and holding power to the rough surface, the amount of the monomer A2 used is preferably 3.5% by weight or more, more preferably 4% by weight or more, and still more preferably 4.5% by weight. the above. From the viewpoint of improving the adhesion and holding force to the rough surface, the use amount of the monomer A2 is preferably 48% by weight or less, more preferably 45% by weight or less, and even more preferably 40% by weight. % By weight or less.

The total ratio of the monomers A1 and A2 may be, for example, 75% by weight or more of all the monomer components. From the viewpoint of further improving the adhesion and holding power of the adherend having a rough surface, the total ratio of the monomer A1 to the monomer A2 is preferably 80% by weight or more of all monomer components, and more preferably 85% by weight. % Or more, and more preferably 90% by weight or more.

＜ functional monomers ＞
The monomer component forming the (meth) acrylic polymer may include at least one functional group-containing monomer selected from the group consisting of a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group. body. By including such a functional group-containing monomer, the flexibility of the resin layer can be maintained, and an interconnection network can be formed to control the interaction between molecules. The cohesion of the resin layer can be improved and a higher retention force can be exhibited. The monomer component may include, for example, a monomer having a hydroxyl group and a monomer having a carboxyl group.

As the monomer having a hydroxyl group (a hydroxyl-containing monomer), a polymerizable functional group having an unsaturated double bond such as a (meth) acrylfluorenyl group or a vinyl group and a hydroxyl group can be used without particular limitation. Examples of the hydroxyl-containing monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4- Hydroxybutyl, 6-hydroxyhexyl (meth) acrylate, 8-hydroxyoctyl (meth) acrylate, 10-hydroxydecyl (meth) acrylate, 12-hydroxylauryl (meth) acrylate, etc. Hydroxyalkyl acrylate; hydroxyalkylcycloalkane (meth) acrylate such as (4-hydroxymethylcyclohexyl) methyl (meth) acrylate and the like. Examples of other hydroxyl-containing monomers include hydroxyethyl (meth) acrylamide, allyl alcohol, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and diethylene glycol monovinyl ether. The hydroxyl group-containing monomers may be used singly or in combination of two or more kinds. Among them, hydroxyalkyl (meth) acrylate is preferred, and 2-hydroxyethyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate are particularly preferred.

As the monomer having a carboxyl group (carboxyl group-containing monomer), a polymerizable functional group having an unsaturated double bond such as a (meth) acrylfluorenyl group or a vinyl group and a carboxyl group can be used without particular limitation. Examples of the carboxyl group-containing monomer include (meth) acrylic acid, carboxyethyl (meth) acrylate, carboxypentyl (meth) acrylate, itaconic acid, maleic acid, fumaric acid, Butenoic acid, methacrylic acid, etc. The carboxyl group-containing monomers may be used alone or in combination of two or more. Among these, acrylic acid and methacrylic acid are preferred, and acrylic acid is particularly preferred.

As the above-mentioned monomer having an epoxy group (epoxy-containing monomer), a polymerizable functional group having an unsaturated double bond, such as a (meth) acrylfluorenyl group or a vinyl group, and having a ring can be used without particular limitation. Oxygen. Examples of the epoxy group-containing monomer include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl methyl (meth) acrylate, and 4-hydroxybutyl (meth) acrylate glycidyl ether. Wait. The epoxy group-containing monomer may be used singly or in combination of two or more kinds.

From the viewpoint of improving cohesion, when the hydroxyl-containing monomer is used, the amount used is preferably 0.01% by weight or more, and more preferably 0.03% by weight or more, of all monomer components forming the (meth) acrylic polymer. From the viewpoint of suppressing excessive viscosity increase or gelation, the amount of the hydroxyl-containing monomer used is preferably 20% by weight or less, preferably 15% by weight or less, more preferably 10% by weight or less, It is more preferably 5 wt% or less, still more preferably 3 wt% or less, and even more preferably 2 wt% or less.

From the viewpoint of improving cohesion and imparting interaction with the molecular level on the surface of the adherend, when using a carboxyl group-containing monomer, the amount used is preferably all that forms a (meth) acrylic polymer. The monomer component is 0.1% by weight or more, and more preferably 0.2% by weight or more. From the viewpoint of improving the followability to the rough surface or maintaining the adhesion at a low temperature, the use amount of the carboxyl group-containing monomer is preferably 5% by weight or less of the aforementioned monomer component, and more preferably 3% by weight or less, more preferably 2.6% by weight or less, and particularly preferably 2.2% by weight or less.

From the viewpoint of improving cohesion, when the epoxy group-containing monomer is used, the amount used is preferably 0.1% by weight or more, and more preferably 0.2% by weight, of all monomer components forming the (meth) acrylic polymer. the above. From the viewpoint of suppressing gelation or high viscosity, the amount of the epoxy-containing monomer used is preferably 1% by weight or less, and more preferably 0.5% by weight or less. When the (meth) acrylic polymer is a graft polymer, it is not limited to this.

When a hydroxyl-containing monomer and a carboxyl-containing monomer are used together as the functional group-containing monomer, from the viewpoint of improving the adhesion to a substrate having a rough surface, the hydroxyl-containing monomer and the carboxyl-containing monomer The weight ratio (hydroxyl-containing monomer / carboxyl-containing monomer) is preferably 0.01 or more, more preferably 0.02 or more, still more preferably 1.0 or less, and more preferably 0.50 or less.

＜ Co-monomers ＞
In addition to the monomers A1 and A2, the monomer components forming the (meth) acrylic polymer may optionally include copolymerized monomers (equivalent to monomer A1 or monomers) other than the functional group-containing monomers. Except for A2). The copolymerizable monomers may be used singly or in combination of two or more kinds.

Examples of the copolymerizable monomer include a monomer represented by the general formula (2): CH ₂ = CR ³ -COO-R ⁴ ; Here, R ³ in the general formula (2) is a hydrogen atom or a methyl group. R ⁴ is an unsubstituted alkyl group or a substituted alkyl group having 1 to 24 carbon atoms.

The unsubstituted alkyl group or substituted alkyl group having 1 to 24 carbon atoms (more preferably 1 to 18 carbon atoms) as R ⁴ in the above-mentioned general formula (2) represents a linear or branched alkyl group, Or cyclic cycloalkyl. Specifically, R ⁴ may be a linear alkyl group having 1 to 18 carbon atoms, a branched alkyl group having 3 to 7 carbon atoms, or a cyclic alkyl group. In the case where R ⁴ is a substituted alkyl group, examples of preferred substituents include an aryl group having 3 to 7 carbon atoms or an aryloxy group having 3 to 7 carbon atoms. Although it does not specifically limit as said aryl group, For example, a phenyl group is preferable.

Examples of the monomer represented by the general formula (2) include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, and (meth) acrylic acid second Butyl ester, third butyl (meth) acrylate, isobutyl (meth) acrylate, n-amyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, (formyl) (Heptyl) heptyl acrylate, isoamyl (meth) acrylate, n-octyl (meth) acrylate, n-nonyl (meth) acrylate, phenoxyethyl (meth) acrylate, benzyl (meth) acrylate Ester, cyclohexyl (meth) acrylate, 3,3,5-trimethylcyclohexyl (meth) acrylate, isopropyl (meth) acrylate, terpene (meth) acrylate, (meth) ) Dicyclopentyl acrylate and the like.

As the comonomer, for example, ethylene such as vinyl acetate, vinyl propionate, styrene, α-methylstyrene, N-vinyl caprolactam, and N-vinylpyrrolidone can be used. Basic monomers; (meth) acrylic acid esters such as tetrahydrofurfuryl (meth) acrylate, fluoro (meth) acrylate, polysiloxane (meth) acrylate, or 2-methoxyethyl acrylate Body; cyano group-containing monomers such as (meth) acrylonitrile; in addition, fluorenylamine-containing monomers, amine-containing monomers, fluorenimine-containing monomers, N-acrylamidoline, ethylene Ether monomers, etc.

As another example of the above-mentioned copolymerized monomer, a silane-based monomer containing a silicon atom and the like can be mentioned. Examples of the silane-based monomer include 3-propenyloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 4-vinylbutyltrimethoxysilane, 4-vinylbutyltriethoxysilane, 8-vinyloctyltrimethoxysilane, 8-vinyloctyltriethoxysilane, 10-methacryloxydecyltrimethoxysilane, 10-propenyloxydecyltrimethoxysilane, 10-methacryloxydecyltriethoxysilane, 10-propenyloxydecyltriethoxysilane, and the like.

The usage-amount of the said copolymerization monomer is 20 weight% or less of all the monomer components which form a (meth) acrylic-type polymer, Preferably it is 15 weight% or less. When the content of the comonomer exceeds 20% by weight, for example, the adhesion to the rough surface may be reduced.

＜ Polyfunctional monomer ＞
The monomer component forming the (meth) acrylic polymer may contain a polyfunctional monomer, if necessary, for the purpose of preparing cohesiveness and the like. The polyfunctional monomer may be used singly or in combination of two or more kinds.

The above-mentioned polyfunctional single system is a monomer having at least two polymerizable functional groups ((meth) acrylfluorenyl group, vinyl group, etc.) having an unsaturated double bond, and examples thereof include (poly) ethylene glycol di ( (Meth) acrylate, (poly) propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,12-dodecanediol di (methyl) (Meth) acrylate esters of polyhydric alcohols such as acrylate, trimethylolpropane tri (meth) acrylate, tetramethylolmethane tri (meth) acrylate, and (meth) acrylic acid; allyl (meth) acrylate Ester, vinyl (meth) acrylate, divinylbenzene, epoxy acrylate, polyester acrylate, urethane acrylate, butyl di (meth) acrylate, hexyl di (meth) acrylate, etc. . Among these, trimethylolpropane tri (meth) acrylate, hexanediol di (meth) acrylate, and dipentaerythritol hexa (meth) acrylate are preferred.

The polyfunctional monomer may be used in an amount of 5% by weight or less based on all the monomer components forming the (meth) acrylic polymer. The said polyfunctional monomer differs according to its molecular weight, the number of functional groups, etc., It is preferable that it is 3 weight% or less with respect to all the monomer components which form a (meth) acrylic-type polymer, and it is still more preferable that it is 2 weight% or less. If the content of the polyfunctional monomer is too large, for example, the elastic modulus of the resin composition may become too high, and the adhesion to the rough surface (especially the adhesion in a low temperature range) may be reduced.

＜ (Meth) acrylic polymer and its production method ＞
The Tg of the (meth) acrylic polymer is -40 ° C or lower. From the viewpoint of improving the adhesion to an adherend having a rough surface, the Tg of the (meth) acrylic polymer is preferably -45 ° C or lower, more preferably -50 ° C or lower. From the viewpoint of improving the adhesion at low temperature, in some aspects, the Tg of the (meth) acrylic polymer is, for example, preferably -55 ° C or lower, more preferably -57 ° C or lower, and even more preferably Below -60 ° C. Moreover, from a viewpoint of improving the adhesive force and holding force with respect to the adherend which has a rough surface, Tg of the said (meth) acrylic-type polymer becomes like this. Preferably it is -85 degreeC or more, More preferably, it is -80 degreeC or more.

Here, the Tg of the (meth) acrylic polymer is a theoretical value calculated based on the composition of monomer components constituting the (meth) acrylic polymer based on the following formula of Fox.
Fox's formula: 1 / Tg = W ₁ / Tg ₁ ＋ W ₂ / Tg ₂ ＋ ・ ・ ・ ＋ W _n / Tg _n
[In the formula, Tg is the glass transition temperature (unit: K) of the (meth) acrylic polymer, and Tg _i (i = 1, 2, ...) is the glass transition when the monomer i forms a homopolymer temperature _{(unit: K), W i (i} = 1,2, · · · n) represents the mass fraction of the monomer i in all of the monomer component]

The manufacturing method of the said (meth) acrylic-type polymer is not specifically limited, A well-known manufacturing method can be selected suitably. For example, various radical polymerization methods such as solution polymerization, radiation polymerization by electron beam or ultraviolet (UV) irradiation, block polymerization, and emulsion polymerization can be used. The obtained (meth) acrylic polymer may be any of a random copolymer, a block copolymer, and a graft copolymer.

In the above-mentioned radical polymerization, a known polymerization initiator, a chain transfer agent, an emulsifier, a polymerization solvent, and the like may be used as necessary according to the state of polymerization. In addition, the Mw of the (meth) acrylic polymer can be controlled by a polymerization initiator, a chain transfer agent, reaction conditions, and the like, and an appropriate amount thereof can be adjusted according to the types of these.

In the solution polymerization, as the polymerization solvent, for example, ethyl acetate, toluene, or a mixed solvent thereof can be used. The above-mentioned solution polymerization is carried out, for example, under a gas flow of inert gas such as nitrogen and adding a polymerization initiator, usually at a temperature of about 50 to 70 ° C. and under reaction conditions of about 5 to 30 hours.

Examples of the polymerization initiator include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis (2-fluorenylpropane) dihydrochloride, and 2,2 ' -Azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-Azobis (2-methylpropionamidine) disulfate, 2 , 2'-Azobis (N, N'-dimethylmethylene isobutylphosphonium), 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropylhydrazone] hydrate Compounds (manufactured by Wako Pure Chemical Industries, VA-057) and other azo initiators; persulfates such as potassium persulfate and ammonium persulfate; bis (2-ethylhexyl) peroxydicarbonate, peroxydicarbonate Di (4-third butylcyclohexyl) ester, di-second butyl peroxydicarbonate, tertiary butyl peroxydecanoate, tertiary hexyl pervalerate, tertiary pervalerate Tributyl ester, dilauryl peroxide, di-n-octyl peroxide, 1,1,3,3-tetramethylbutyl-2-ethylhexanoate, di (4-methylbenzene peroxide) (Methylamino), dibenzoylperoxide, tert-butyl isobutyrate, 1,1-bis (tertiary hexyl peroxide) cyclohexane, tertiary butyl hydroperoxide, hydrogen peroxide, etc. Peroxide-based initiator; persulfate and Oxidizing composition as sodium bisulfite, sodium peroxide composition of ascorbate in combination with a reducing agent of a peroxide redox initiator and so forth, but are not limited to such. In several aspects, AIBN can be preferably used as a polymerization initiator.

The polymerization initiators may be used singly or in combination of two or more. The amount of the polymerization initiator used is usually about 0.005 to 1 part by weight, and more preferably about 0.01 to 0.5 part by weight, based on 100 parts by weight of the monomer component.

Examples of the chain transfer agent include lauryl mercaptan, glycidyl mercaptan, thioglycolic acid, 2-mercaptoethanol, thioglycolic acid, 2-ethylhexyl thioglycolate, and 2,3-dimercapto- 1-propanol and the like. The chain transfer agent may be used singly or in combination of two or more kinds. The amount of the chain transfer agent used is preferably set to about 0.1 parts by weight or less based on 100 parts by weight of the total amount of the monomer components. Alternatively, a chain transfer agent may not be used.

Emulsion polymerization is typically performed using a known emulsifier. Examples of the emulsifier include anionic emulsifiers such as sodium lauryl sulfate, lauryl ammonium sulfate, sodium dodecylbenzenesulfonate, polyoxyethylene alkyl ether ammonium sulfate, and polyoxyethylene alkylphenyl ether sodium sulfate. Agent; non-ionic emulsifiers such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene fatty acid ester, polyoxyethylene-polyoxypropylene block polymer, etc.

As the emulsifier, an emulsifier into which a radical polymerizable functional group such as an propylene group or an allyl ether group is introduced can be used. Such an emulsifier having a polymerizable functional group introduced is also sometimes referred to as a reactive emulsifier. Specific examples of the reactive emulsifier include: AQUALON HS-10, HS-20, KH-10, BC-05, BC-10, BC-20 (the above are all manufactured by Daiichi Pharmaceutical Co., Ltd.); ADEKA REASOAP SE10N (manufactured by ADEKA). Since a reactive emulsifier is introduced into a polymer chain after polymerization, water resistance is improved, which is preferable.

Emulsifiers can be used alone or in combination of two or more. The amount of the emulsifier to be used is preferably about 0.3 to 5 parts by weight relative to 100 parts by weight of the monomer component. In terms of polymerization stability or mechanical stability, it is preferably set to about 0.5 to 1 part by weight.

When the (meth) acrylic polymer is produced by radiation polymerization, it can be produced by polymerizing the monomer component by irradiating radiation such as an electron beam and UV. When the above-mentioned radiation polymerization is performed by an electron beam, it is not particularly necessary that the above-mentioned monomer component contains a photopolymerization initiator. When the above-mentioned radiation polymerization is performed by UV polymerization, from the viewpoint of shortening the polymerization time, it is preferred that the monomer component contains a photopolymerization initiator. The photopolymerization initiators may be used alone or in combination of two or more.

The photopolymerization revealing agent is not particularly limited as long as it can initiate photopolymerization, and it can be appropriately selected from various known photopolymerization initiators and used. For example, benzoin ether type, acetophenone type, α-keto alcohol type, photoactive oxime type, benzoin type, diphenylethylenedione type, benzophenone type, ketal type, 9-oxysulfide can be used. Is a photopolymerization initiator. The used amount of the photopolymerization initiator is 0.05 to 1.5 parts by weight, and preferably 0.1 to 1 part by weight based on 100 parts by weight of the monomer component.

In some aspects, the weight average molecular weight (Mw) of the (meth) acrylic polymer is preferably 350,000 or more. From the viewpoint of improving the durability and cohesiveness of the resin layer, the Mw of the (meth) acrylic polymer is more preferably 400,000 or more, and even more preferably 500,000 or more. From the viewpoint of improving the adhesion at a low temperature or suppressing the increase in viscosity of the resin composition, the Mw of the (meth) acrylic polymer is preferably 3 million or less, more preferably 2.5 million or less, and more It is preferably 2 million or less, further preferably 1.5 million or less, and even more preferably 1.2 million or less.

The Mw of the (meth) acrylic polymer can be measured by GPC (Gel Permeation Chromatography) under the following conditions, and calculated by polystyrene conversion. A sample for GPC was a filtrate obtained by dissolving a sample in tetrahydrofuran (THF) to make a 0.1% by weight solution, leaving it to stand overnight, and filtering it through a 0.45 μm membrane filter. The same method is also used in the following examples.
・ Analytical device: manufactured by Tosoh Corporation, HLC-8120GPC
・ Column: Made by Tosoh Corporation, GM7000HXL ＋ GMHXL ＋ GMHXL
・ Pipe size: each 7.8 mmf × 30 cm (total 90 cm)
・ Sample concentration: 0.1% by weight (THF solution)
・ Eluent: THF
・ Flow rate: 0.8 ml / min
・ Inlet pressure: 1.6 MPa
・ Detector: Differential refractometer (RI)
・ Column temperature: 40 ℃
・ Injection volume: 100 μl
・ Standard sample: polystyrene

＜ crosslinking agent ＞
The resin composition disclosed herein may contain a crosslinking agent as needed. Examples of the cross-linking agent include an isocyanate-based cross-linking agent, an epoxy-based cross-linking agent, a polysiloxane-based cross-linking agent, an oxazoline-based cross-linking agent, an aziridine-based cross-linking agent, a silane-based cross-linking agent, and an alkane. Cross-linking agents such as methyl etherified melamine-based cross-linking agents, metal chelator-based cross-linking agents, and peroxides are not limited thereto. As a preferable example of the said crosslinking agent, an isocyanate type crosslinking agent and an epoxy type crosslinking agent are mentioned. An isocyanate-based crosslinking agent and an epoxy-based crosslinking agent may be used in combination.

These crosslinking agents may be used alone or in combination of two or more. The use amount of the crosslinking agent is preferably in a range of 0.005 parts by weight to 10 parts by weight based on 100 parts by weight of the (meth) acrylic polymer. The content of the crosslinking agent with respect to 100 parts by weight of the (meth) acrylic polymer is preferably 0.01 parts by weight or more and 4 parts by weight or less, more preferably 0.02 parts by weight or more and 3 parts by weight or less, and still more preferably 0.05 weight. Or more and not more than 2 parts by weight. Moreover, you may use the said polyfunctional monomer as a crosslinking agent. In this case, the use amount of the polyfunctional monomer is preferably set to a range of 0.001 to 2 parts by weight relative to 100 parts by weight of the (meth) acrylic polymer, and more preferably The range is 0.003 parts by weight or more and 1 part by weight or less.

As the isocyanate-based crosslinking agent, a compound having two or more isocyanate groups in one molecule (which may be an isocyanate-regenerating functional group that temporarily protects the isocyanate group by a blocking agent, polymerization, or the like) may be used. . Examples of the isocyanate-based crosslinking agent include aromatic isocyanates such as toluene diisocyanate and xylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate.

Specific examples of the isocyanate-based crosslinking agent include lower aliphatic polyisocyanates such as butylene diisocyanate and hexamethylene diisocyanate; cyclopentyl diisocyanate, cyclohexane diisocyanate, and isocyanate. Aliphatic isocyanates such as phorone diisocyanate; aromatic aromatics such as 2,4-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, polymethylene polyphenyl isocyanate Diisocyanates; trimethylolpropane / toluene diisocyanate terpolymer adduct (manufactured by Tosoh Corporation, trade name: Coronate L), trimethylolpropane / hexamethylene diisocyanate terpolymer adduct (Manufactured by Tosoh Corporation, trade name: Coronate HL), isocyanurate of hexamethylene diisocyanate (manufactured by Tosoh Corporation, trade name: Coronate HX), and other isocyanate adducts; xylylene diisocyanate Trimethylolpropane adduct (manufactured by Mitsui Chemicals, trade name: Takenate D110N), trimethylol propane adduct of xylylene diisocyanate (manufactured by Mitsui Chemicals, trade name: Takenat e D120N), trimethylolpropane adduct of isophorone diisocyanate (made by Mitsui Chemicals, trade name: Takenate D140N), trimethylolpropane adduct of hexamethylene diisocyanate (Mitsui Chemical Manufactured by the company, trade name: Takenate D160N), polyether polyisocyanate, polyester polyisocyanate, and the addition products with various polyols, through isocyanurate bond, biuret bond, ureidoformic acid A polyisocyanate or the like obtained by multifunctionalizing an ester bond or the like. Among these, in order to better balance the properties related to adhesion and holding force, it is preferable to use an aromatic isocyanate or an alicyclic isocyanate.

The isocyanate-based crosslinking agent may be used singly or in combination of two or more kinds. The usage-amount of an isocyanate crosslinking agent is 0.01 weight part or more and 10 weight part or less with respect to 100 weight part of (meth) acrylic-type polymers, Preferably it is usually 0.03 weight part or more and 8 weight part or less. It is more preferably set to 0.05 parts by weight or more and 6 parts by weight or less, or 0.08 parts by weight or more and 5 parts by weight or less. The amount of the isocyanate cross-linking agent to be used may be appropriately set in consideration of cohesive force and prevention of peeling in the durability test.

From the viewpoint that the composition containing the adhesion-imparting resin can easily exhibit good adhesion even at low temperatures, in some aspects, the isocyanate crosslinking agent is used with respect to 100 parts by weight of the (meth) acrylic polymer. The amount may be less than 5.0 parts by weight, preferably less than 4.0 parts by weight, more preferably less than 3.0 parts by weight, even more preferably less than 2.0 parts by weight, even more preferably less than 1.5 parts by weight, and even more preferably less than Up to 1.0 part by weight. In addition, from the viewpoint of easily exhibiting a good holding power in a composition containing an adhesion-imparting resin, in some aspects, the use amount of the isocyanate crosslinking agent is, for example, preferably 0.10 parts by weight or more, and more preferably 0.20 weight. More than.

When an aqueous resin composition (for example, a resin composition containing an aqueous dispersion of a (meth) acrylic polymer prepared by emulsion polymerization) is contained in an isocyanate-based crosslinking agent, the isocyanate-based resin is suppressed. From the viewpoint of improving the storage stability of the resin composition by the reaction of the cross-linking agent with water, an isocyanate cross-linking agent that is temporarily protected by a blocking agent or polymerization, etc., can be used. Alternatively, an isocyanate-based crosslinking agent may not be used.

As the epoxy-based crosslinking agent, a polyfunctional epoxy compound having two or more epoxy groups in one molecule can be used. Examples of the epoxy-based crosslinking agent include N, N, N ', N'-tetraglycidyl-m-xylylenediamine, diglycidylaniline, and 1,3-bis (N, N-di Glycidylaminomethyl) cyclohexane, 1,6-hexanediol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol Glycidyl ether, polypropylene glycol diglycidyl ether, sorbitol polyglycidyl ether, glycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, polyglycerol polyglycidyl ether, sorbitan polyglycidyl ether, trimethylol Polypropane glycidyl ether, diglycidyl adipate, diglycidyl phthalate, triglycidyl-tris (2-hydroxyethyl) isocyanurate, resorcinol diglycidyl Examples of the ether and bisphenol-S-diglycidyl ether include epoxy resins having two or more epoxy groups in the molecule. As a commercial item of the said epoxy-type crosslinking agent, the brand name "Tetrad C" and "Tetrad X" made by Mitsubishi Gas Chemical Co., Ltd. are mentioned, for example.

The epoxy-based crosslinking agent may be used singly or in combination of two or more kinds. The amount of the epoxy-based cross-linking agent may be, for example, 0.005 parts by weight or more and 1 part by weight or less based on 100 parts by weight of the (meth) acrylic polymer, or may be 0.01 part by weight or more and 0.5 parts by weight. It is about 0.015 weight part or more and about 0.3 weight part or less. The usage-amount of an epoxy-type crosslinking agent can be set suitably considering the cohesion and durability.

As the above-mentioned peroxide, as long as a radically active species can be generated by heating and the (meth) acrylic polymer of the resin composition is crosslinked, it can be appropriately used, taking workability or stability into consideration, It is preferable to use a peroxide having a half-life temperature of 80 ° C to 160 ° C for 1 minute, and more preferably to use a peroxide of 90 ° C to 140 ° C.

Examples of the peroxide include bis (2-ethylhexyl) peroxydicarbonate (1 minute half-life temperature: 90.6 ° C), and bis (4-third butylcyclohexyl) peroxydicarbonate ( 1 minute half-life temperature: 92.1 ° C), di-second butyl peroxydicarbonate (1 minute half-life temperature: 92.4 ° C), third butyl peroxy neodecanoate (1 minute half-life temperature: 103.5 ° C), peroxide Tert-hexyl pivalate (1 minute half-life temperature: 109.1 ° C), tert-butyl pervalerate (1-minute half-life temperature: 110.3 ° C), dilaurin peroxide (1-minute half-life temperature: 116.4 ° C) , Di-n-octyl peroxide (1 minute half-life temperature: 117.4 ° C), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (1 minute half-life temperature: 124.3 ° C), Di (4-methylbenzidine) peroxide (1 minute half-life temperature: 128.2 ° C), Dibenzophene peroxide (1 minute half-life temperature: 130.0 ° C), tert-butyl isobutyrate peroxide (1 minute Half-life temperature: 136.1 ° C), 1,1-bis (third hexyl peroxide) cyclohexane (1 minute half-life temperature: 149.2 ° C), and the like. Among them, especially in terms of excellent cross-linking reaction efficiency, bis (4-tert-butylcyclohexyl) dicarbonate (1 minute half-life temperature: 92.1 ° C), dilaurin peroxide can be preferably used. (1 minute half-life temperature: 116.4 ° C), benzophenone peroxide (1 minute half-life temperature: 130.0 ° C), and the like.

It should be noted that the half-life of the above-mentioned peroxide is an index indicating the decomposition rate of the peroxide, and means the time until the residual amount of the peroxide becomes half. The decomposition temperature used to obtain the half-life at any time, or the half-life time at any temperature is described in the manufacturer's catalogue, for example, in the "Organic Peroxide Catalogue 9th Edition ( May 2003) "and so on.

These peroxides may be used alone or in combination of two or more. The amount of the peroxide used is preferably about 0.02 to 2 parts by weight, and preferably about 0.05 to 1 part by weight, based on 100 parts by weight of the (meth) acrylic polymer. The amount of peroxide used is appropriately selected within this range in order to adjust processability, secondary processability, crosslinking stability, and peelability.

The amount of peroxide remaining after the reaction treatment can be grasped, for example, by measuring the amount of peroxide decomposition by HPLC (high performance liquid chromatography). Specifically, for example, a sample of about 0.2 g is collected from the resin layer after the reaction treatment, immersed in 10 ml of ethyl acetate, and extracted with a shaker at 25 ° C and 120 rpm for 3 hours, and then allowed to stand at room temperature. Set for 3 days. Next, 10 ml of acetonitrile can be added and shaken at 120 rpm for 30 minutes at 25 ° C., and then filtered through a membrane filter (0.45 μm) to obtain an extraction solution. About 10 μl of the obtained extraction solution is injected into the HPLC to perform Analyze and set the amount of peroxide after the reaction treatment.

As the metal chelating agent-based crosslinking agent, a polyfunctional metal chelating agent in which a polyvalent metal and an atom in an organic compound are covalently bonded or coordinated may be used. Examples of the polyvalent metal include Al, Cr, Zr, Co, Cu, Fe, Ni, V, Zn, In, Ca, Mg, Mn, Y, Ce, Sr, Ba, Mo, La, Sn, Ti Wait. Examples of the atom in an organic compound that is covalently bonded or coordinated to such a polyvalent metal include an oxygen atom and the like. Examples of the organic compound include an alkyl ester, an alcohol compound, a carboxylic acid compound, an ether compound, and a ketone compound.

<Adhesion imparting resin>
The adhesion-imparting resin used in the resin composition disclosed herein is not particularly limited, and can be appropriately selected from known adhesion-imparting resins. For example, rosin-based adhesion-imparting resin, terpene-based adhesion-imparting resin, phenol-based adhesion-imparting resin, hydrocarbon-based adhesion-imparting resin, ketone-based adhesion-imparting resin, polyamide-based adhesion-imparting resin, epoxy-based adhesion-imparting resin, The elastic system is provided with adhesive and the like. The adhesion-imparting resin may be used alone or in combination of two or more.

Examples of the rosin-based adhesion-imparting resin include unmodified rosin (raw rosin) such as rosin gum, wood rosin, tall oil rosin, or the unmodified rosin is modified by polymerization, disproportionation, and hydrogenation. The resulting modified rosin (polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, or other chemically modified rosin, etc.) may include various rosin derivatives.
Examples of the rosin derivative include: a rosin phenol resin obtained by adding phenol to an rosin (unmodified rosin, modified rosin, various rosin derivatives, etc.) using an acid catalyst and subjecting it to thermal polymerization;
Rosin ester compound (unmodified rosin ester) obtained by esterifying unmodified rosin with alcohol; or polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin by alcohol Rosin ester resins such as modified rosin ester compounds (polymerized rosin esters, stabilized rosin esters, disproportionated rosin esters, fully hydrogenated rosin esters, partially hydrogenated rosin esters, etc.) that are esterified with other modified rosins;
Unsaturated fatty acid modified rosin-based resin modified by unsaturated fatty acids by modifying unmodified rosin or modified rosin (polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, etc.);
Unsaturated fatty acid modified rosin ester resin modified by unsaturated fatty acid rosin ester resin;
For unmodified rosin, modified rosin (polymerized rosin, stabilized rosin, disproportionated rosin, fully hydrogenated rosin, partially hydrogenated rosin, etc.), unsaturated fatty acid modified rosin resin or unsaturated fatty acid modified rosin ester resin Rosin alcohol resin made by reducing carboxyl group;
Metal salts of rosin resins (especially rosin ester resins) such as unmodified rosin, modified rosin, and various rosin derivatives.

Examples of the terpene-based adhesion-imparting resin include terpene-based resins such as α-pinene polymer, β-pinene polymer, and dipentene polymer; or these terpene-based resins are modified (phenol Modified terpene resin (such as terpene phenol resin, styrene modified terpene resin, aromatic modified terpene resin) Resin, hydrogenated terpene-based resin, etc.).

Examples of the phenol-based adhesion-imparting resin include condensates of various phenols (for example, phenol, m-cresol, 3,5-xylenol, p-alkylphenol, and resorcinol) and formaldehyde (for example, alkyl groups). Phenol-based resins, xylene-formaldehyde-based resins, etc.); soluble phenolic resins obtained by the addition reaction of the above phenols and formaldehyde by an alkali catalyst; or condensation reactions of the above phenols and formaldehyde by an acid catalyst The obtained novolac and the like.

Examples of the hydrocarbon-based adhesion-imparting resin include petroleum-based adhesion-imparting resin or styrene-based adhesion-imparting resin. More specifically, aliphatic hydrocarbon resins, aromatic hydrocarbon resins, aliphatic cyclic hydrocarbon resins, aliphatic and aromatic petroleum resins (styrene-olefin copolymers, etc.), and aliphatics Alicyclic petroleum resin, hydrogenated hydrocarbon resin, lavender resin, lavender-indene resin, and the like.

Examples of commercially available rosin-based adhesion-imparting resins that can be preferably used include PENSEL series of rosin ester-based adhesion-imparting resins manufactured by Arakawa Chemical Industries, Ltd., such as "PENSEL AZ", "PENSEL D-125", "PENSEL D-135", "PENSEL D-160", "PENSEL KK", "PENSEL C", etc. are not limited to these.

Examples of commercially available terpene-based adhesion-imparting resins that can be preferably used are: "YS Polyster T130", "YS Polyster T115", "YS Polyster S145", "YS Polyster G125" manufactured by Yasuhara Chemical Co., Ltd. "," YS Polyster N125 "," YS Polyster U115 "; trade names" Tamanol 803L "," Tamanol 901 "manufactured by Arakawa Chemical Industries;" Sumilite Resin PR-12603 "trade name manufactured by Sumitomo Bakelite; Haritack series and so on manufactured by Mahuacheng, but are not limited to these.

The adhesion-imparting resin is suitably used in a range of 5 parts by weight or more and 40 parts by weight or less based on 100 parts by weight of the (meth) acrylic polymer. By setting the use amount of the adhesion-imparting resin to 5 parts by weight or more, the advantageous effects brought about by the use of the adhesion-imparting resin can be exhibited. In some aspects, the use amount of the adhesion-imparting resin relative to 100 parts by weight of the (meth) acrylic polymer is, for example, preferably 7 parts by weight or more, and more preferably 10 parts by weight or more. Moreover, when the usage-amount of an adhesion-imparting resin is 40 weight part or less, the advantageous effect by using an adhesion-imparting resin can be suppressed, and the fall of the adhesiveness at low temperature can be suppressed. In some aspects, the use amount of the adhesion-imparting resin with respect to 100 parts by weight of the (meth) acrylic polymer is, for example, preferably 38 parts by weight or less, and more preferably 35 parts by weight or less.

The softening point (softening temperature) provided by the adhesion to the resin is not particularly limited. From the viewpoint of easily exhibiting good adhesion even at low temperatures, in some aspects, the softening point of the adhesion-imparting resin is preferably 180 ° C or lower, more preferably 160 ° C or lower, or 150 ° C or lower, Below 140 ° C or below 135 ° C. From the viewpoint of suppressing a decrease in cohesive force in a temperature region above room temperature, in some aspects, the softening point of the adhesion-imparting resin is preferably 60 ° C or higher, preferably 80 ° C or higher, and more preferably 90 ° C or higher. The technique disclosed herein can be preferably implemented using an adhesion-imparting resin having a softening point in a range of 90 ° C to 160 ° C, a range of 90 ° C to 150 ° C, or a range of 90 ° C to 140 ° C. When a plurality of types of adhesion-imparting resins having different softening points are used, it is preferable that at least one adhesion-imparting resin has the above-mentioned softening point. For example, it is preferable that 50% by weight or more, 70% by weight or more, 90% by weight or more, or 100% by weight of the total amount of the adhesion-imparting resin has the above-mentioned softening point. The softening point of the adhesion-imparting resin can be measured using a value described in the manufacturer's catalog or based on a softening point test method (ring and ball method) specified in JIS K2207.

＜ (meth) acrylic oligomer ＞
The resin composition disclosed herein may contain a (meth) acrylic oligomer. Here, the (meth) acrylic oligomer refers to the polymerization of a polymer structure including a monomer unit derived from a monomer having a (meth) acrylfluorene group (that is, a (meth) acrylic monomer). The polymer typically refers to a polymer containing the monomer unit at a ratio of more than 50% by weight. As the (meth) acrylic oligomer, a polymer having a Tg higher than the (meth) acrylic polymer and a Mw smaller than the (meth) acrylic polymer can be preferably used. The (meth) acrylic oligomer can improve the adhesion of the adherend such as a rough surface or a plastic.

The (meth) acrylic oligomer preferably has a Tg of about 0 ° C to 300 ° C, preferably about 20 ° C to 300 ° C, and more preferably about 40 ° C to 300 ° C. If the Tg does not reach about 0 ° C, the cohesive force of the resin layer may be reduced in a temperature range of room temperature or higher, and the retention characteristics or the adhesiveness at high temperatures may be reduced. The Tg of the (meth) acrylic oligomer is a theoretical value calculated based on the formula of Fox in the same manner as the Tg of the (meth) acrylic polymer.

The Mw of the (meth) acrylic oligomer may be, for example, 1,000 or more and less than 30,000, preferably 1,500 or more and less than 20,000, and more preferably 2,000 or more and less than 10,000. If Mw is 30,000 or more, there is a case where the effect of improving the adhesion cannot be sufficiently obtained. Moreover, if Mw is less than 1,000, it will become a low molecular weight, and may cause a fall of adhesive force or retention characteristics.
Mw of a (meth) acrylic-type oligomer can be calculated | required based on the polystyrene conversion value of GPC. Specifically, the measurement can be performed on HPLC8020 manufactured by Tosoh Corporation using two TSKgel GMH-H (20) as a column and a THF solvent at a flow rate of about 0.5 ml / minute.

Examples of the monomer constituting the (meth) acrylic oligomer include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, and (meth) acrylic acid. Propyl ester, butyl (meth) acrylate, isobutyl (meth) acrylate, second butyl (meth) acrylate, third butyl (meth) acrylate, amyl (meth) acrylate, (formyl) Base) isoamyl acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate Ester, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, undecyl (meth) acrylate, (meth) ) Alkyl (meth) acrylates such as dodecyl acrylate; cyclohexyl (meth) acrylate, isopropyl (meth) acrylate, dicyclopentyl (meth) acrylate and the like ( Esters of meth) acrylic acid and alicyclic alcohols; phenyl (meth) acrylates, aryl (meth) acrylates, such as benzyl (meth) acrylates; (a) Base) acrylate, etc. (Meth) acrylate. Such (meth) acrylates can be used alone or in combination of two or more.

The (meth) acrylic oligomer is preferably a (meth) acrylic alkyl group having a branched structure with an alkyl group such as isobutyl (meth) acrylate or third butyl (meth) acrylate. Esters; (meth) acrylic acid and alicyclic alcohols, such as cyclohexyl (meth) acrylate or isopropyl (meth) acrylate, dicyclopentyl (meth) acrylate; (meth) acrylic acid Acrylic monomers having a relatively large structure such as (meth) acrylates having a cyclic structure such as phenyl esters or aryl (meth) acrylates such as benzyl (meth) acrylate and the like have a relatively large volume as a unit. Body unit. When the (meth) acrylic oligomer has such a large volume structure, the adhesion of the resin layer can be further improved. Especially in terms of larger volume, those with a ring structure have a higher effect, and those with a plurality of rings have a higher effect. When UV is used in the synthesis of a (meth) acrylic oligomer or in the production of a resin layer, it is preferable to use an alcohol and ( (Meth) acrylic acid esters of (meth) acrylic acid. For example, an (meth) acrylic acid alkyl ester having a branched structure in the alkyl group, or an alicyclic alcohol and (meth) acrylic acid ester can be preferably used as a monomer constituting the (meth) acrylic oligomer.

In this regard, examples of preferred (meth) acrylic oligomers include cyclohexyl methacrylate (CHMA), dicyclopentyl acrylate (DCPA), and dicyclopentyl methacrylate ( DCPMA), isopropyl acrylate (IBXA), isopropyl methacrylate (IBXMA), 1-adamantyl acrylate (ADA), 1-adamantyl methacrylate (ADMA) and other homopolymers; Copolymer of CHMA and isobutyl methacrylate (IBMA), copolymer of CHMA and IBXMA, copolymer of CHMA and acryloline (ACMO), copolymer of CHMA and diethylacrylamide (DEAA), ADA Copolymers with methyl methacrylate (MMA), copolymers of DCPMA and IBXMA, copolymers of DCPMA and MMA, etc. A (meth) acrylic oligomer containing CHMA as a main component is particularly preferred.

When the (meth) acrylic oligomer is used in the resin composition disclosed herein, the amount of use thereof is not particularly limited. In some aspects, the used amount of the (meth) acrylic oligomer is preferably 70 parts by weight or less relative to 100 parts by weight of the (meth) acrylic polymer, and may be, for example, 1 to 70 parts by weight, more It is preferably 2 to 50 parts by weight, and more preferably 3 to 40 parts by weight. When the addition amount of a (meth) acrylic-type oligomer is too much, the elastic modulus may become too high, and the adhesion of the rough surface at low temperature may fall. In addition, by blending 1 part by weight or more of the (meth) acrylic oligomer with respect to 100 parts by weight of the (meth) acrylic polymer, the effect of improving the adhesion can be exhibited better. The technique disclosed here can be preferably implemented even in a form in which a (meth) acrylic oligomer is not used.

＜ Silane coupling agent ＞
The resin composition disclosed herein may contain a silane coupling agent for the purpose of improving the adhesion reliability of the interface with the adherend. Examples of the silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, and 3-glycidoxypropylmethyldiethoxy Silane, 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane, and other epoxy-containing silane coupling agents; 3-aminopropyltrimethoxysilane, N-2- (aminoethyl)- 3-aminopropylmethyldimethoxysilane, 3-triethoxysilyl-N- (1,3-dimethylbutylene) propylamine, N-phenyl-γ-aminopropyl Aminosilane-containing coupling agents such as trimethoxysilane; 3-propenyloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane and other (meth) acrylic acid-containing groups Silane coupling agents; isocyanate-containing silane coupling agents such as 3-isocyanatopropyltriethoxysilane.

When the silane coupling agent is used, the amount used is preferably 1 part by weight or less, for example, 0.01 to 1 part by weight, and more preferably 0.02 to 0.6 part by weight based on 100 parts by weight of the (meth) acrylic polymer. If the silane coupling agent is used in an excessive amount, cross-linking may be inhibited or adhesion characteristics may be impaired. The technique disclosed here can be preferably implemented even without using a silane coupling agent.

In addition, the resin composition disclosed herein may optionally contain other known additives. For example, powders such as colorants, pigments, dyes, surfactants, plasticizers, surface lubricants, leveling agents, softeners, antioxidants, anti-aging agents, light stabilizers, ultraviolet absorbers, Polymerization inhibitor, inorganic or organic filler, metal powder, particle, foil, etc.

＜ Resin layer and laminated sheet ＞
According to the specification, a resin layer formed from any of the resin compositions disclosed herein is provided. The thickness of the resin layer is not particularly limited. The thickness of the resin layer may be, for example, about 1 μm to 1000 μm, preferably about 2 μm to 500 μm, and more preferably 2 μm to 300 μm. From the viewpoint of improving the adhesion or the adhesion to the unevenness of the rough surface, in some aspects, the thickness of the resin layer may be, for example, 5 μm or more, 10 μm or more, 25 μm or more, and may be 35 μm or more, or 50 μm or more or 70 μm or more. From the viewpoint of economy, in some aspects, the thickness of the resin layer may be, for example, 200 μm or less, 150 μm or less, or 100 μm or less. The resin layer disclosed herein may have a single-layer structure or a multilayer structure with two or more layers.

The polymer gel fraction of the resin layer is not particularly limited. From the viewpoint of adhesion to a rough surface, it is generally suitable to be 20 to 98% by weight. In some aspects, the polymer gel fraction of the resin layer may be, for example, 20 to 95% by weight. If the polymer gel fraction of the resin layer is in the above range, there is a tendency that a higher adhesion force and a higher retention force are better exhibited. The reason is presumed to be that if the polymer gel fraction of the resin layer is in the above range, the softness of the resin layer can be maintained, and cohesiveness can be imparted by forming a moderate interconnection network.

From the viewpoint of further improving the cohesiveness or holding power of the resin layer, the polymer gel fraction of the resin layer is, for example, preferably 22% by weight or more, more preferably 25% by weight or more, and even more preferably 30% by weight or more. From the viewpoint of improving the adhesion of the rough surface at a low temperature, the polymer gel fraction of the resin layer is, for example, preferably 90% by weight or less, more preferably 85% by weight or less, and even more preferably 80% by weight or less. It is more preferably 75% by weight or less, and even more preferably 70% by weight or less. When the resin composition contains a cross-linking agent, the total amount of the cross-linking agent can be adjusted, and the gel fraction can be controlled by considering the influence of the cross-linking treatment temperature or the cross-linking treatment time. The polymer gel fraction of the resin layer was measured by the method described in the following examples.

The resin layer disclosed herein preferably has a storage elastic modulus G ′ (23 ° C.) of 1.0 × 10 ⁴ Pa or more and 5.0 × 10 ⁴ Pa or less. When the storage elastic modulus G ′ (23 ° C.) of the resin layer is low, the adhesiveness of the resin layer to the unevenness of the rough surface (the above-mentioned followability to the uneven shape) tends to be higher. When the adhesiveness is high, the contact area between the resin layer and the rough surface becomes large, and the adhesion force is easily increased. From this viewpoint, in some aspects, the storage elastic modulus G ′ (23 ° C.) of the resin layer is preferably 4.8 × 10 ⁴ Pa or less, and more preferably 4.6 × 10 ⁴ Pa or less. From the viewpoint of providing a moderate cohesive force to the resin layer to improve the adhesion or holding force, the storage elastic modulus G '(23 ° C) of the resin layer may be, for example, 1.2 × 10 ⁴ Pa or more, and may be 1.5 × 10 ⁴ Pa or more.

The storage elastic modulus G '(23 ° C) of the resin layer can be measured using a commercially available dynamic viscoelasticity measuring device, and more specifically, it can be measured by a method described in the following Examples. The storage elastic modulus G '(23 ° C) of the resin layer can be adjusted by the composition of the monomer components constituting the acrylic polymer, the use of a cross-linking agent, the use of an adhesion-imparting resin, and the like. For example, by increasing the weight fraction of monomer A2 to monomer components, or further reducing the weight ratio of monomer A1 to monomer A2 (that is, by using more monomer A2 than monomer A1), Reduce the storage elastic modulus G '(23 ° C) of the resin layer. Examples of the monomer A2 having a high effect of lowering the storage elastic modulus G '(23 ° C) include a chain ether bond-containing (meth) acrylate represented by the above-mentioned general formula (1). The Tg of the polymer is -40 ° C or lower (more preferably -45 ° C or lower, even more preferably -50 ° C or lower, such as -55 ° C or lower).

The resin layer disclosed herein preferably has a storage elastic modulus G ′ (-10 ° C.) of 3.0 × 10 ⁴ Pa or more and 7.0 × 10 ⁵ Pa or less. The lower the storage elastic modulus G '(-10 ° C) of the resin layer is from the viewpoint that the unevenness of the resin layer and the rough surface is easily adhered even at low temperatures, and the adhesion of the rough surface at low temperatures is improved. advantageous. From this viewpoint, in some aspects, the storage elastic modulus G ′ (-10 ° C.) of the resin layer is preferably 6.5 × 10 ⁵ Pa or less, more preferably 6.0 × 10 ⁵ Pa or less. In addition, from the viewpoint of avoiding an event of insufficient cohesion at room temperature or above, the storage elastic modulus G ′ (-10 ° C.) of the resin layer may be, for example, 5.0 × 10 ⁴ Pa or more, and may be 7.0. × 10 ⁴ Pa or more. The storage elastic modulus G '(-10 ° C) of the resin layer can be measured in the same manner as the storage elastic modulus G' (23 ° C) using a commercially available dynamic viscoelasticity measuring device, and more specifically, by the following The measurement was performed by the method described in the examples. The storage elastic modulus G '(-10 ° C) of the resin layer can be adjusted by the composition of the monomer components constituting the acrylic polymer, the use of a cross-linking agent, the use of an adhesion-imparting resin, and the like.

The haze value of the resin layer disclosed herein is not particularly limited. For example, when the thickness of the resin layer is 85 μm, the haze value of the resin layer may be 10% or less. In a preferred aspect, the haze value of the resin layer at a thickness of 85 μm is 1.9% or less. Such a laminated sheet having a resin layer having higher transparency is suitable for a use requiring a higher light transmittance in a constitution having a support or a constitution having no support, or is required to be well recognized by the laminated sheet The use of the properties of the adherend. Moreover, it is suitable for the use which requires the property of the external appearance of the said support to be recognized well by the resin layer in the structure which has a support. The haze value of the resin layer at a thickness of 85 μm is more preferably 1.5% or less, further preferably 1% or less, and still more preferably 0.7% or less. The lower limit of the haze value of the resin layer is not particularly limited. For example, the thickness of the resin layer with a thickness of 85 μm may be implemented as a haze value of 0% or more (for example, 0.05% or more).

In the case where the technology disclosed herein is implemented in the form of a laminated sheet with a substrate (support), the haze value of the laminated sheet is not particularly limited. For example, it can be implemented as the haze value of the laminated sheet with a base material is 15% or less. Such a laminated sheet with a substrate having higher transparency is suitable for applications requiring higher light transmittance, or applications in which the properties of the adherend can be recognized well by the laminated sheet. In a preferred aspect, the haze value of the laminated sheet with the substrate is 5% or less, more preferably 1.9% or less, and still more preferably 1.5% or less (for example, 1% or less). The lower limit of the haze value of the laminated sheet with a substrate is not particularly limited. For example, the laminated sheet with a base material may be implemented in a state where the haze value is 0% or more (for example, 0.05% or more).

Here, the "haze value" refers to a ratio of diffused transmitted light to total transmitted light when the measurement target is irradiated with visible light. Also called a haze value. The haze value can be expressed by the following formula.
Th (%) = Td / Tt × 100
In the above formula, Th is a haze value (%), Td is a scattered light transmittance, and Tt is a total light transmittance. The haze value can be measured according to the method described in the following examples.

The resin layer can be formed into a laminated sheet by, for example, applying the resin composition to one or both sides of a support, and removing the polymerization solvent and the like by heating and drying. The support constituting the laminated sheet may be a peelable (that is, a resin layer constituting the laminated sheet described above) support, or may be a non-releasable support. Moreover, after forming a resin layer from the resin composition coated on the peelable support body, this resin layer may be bonded to one or both sides of a non-peelable support body, and a laminated sheet may be comprised. When coating the resin composition, one or more solvents other than the polymerization solvent may be appropriately added for the purpose of improving coating properties or adjusting thickness.

As a coating method of the said resin composition, various methods can be used. Specific examples include: roll coating, contact roll coating, gravure coating, reverse coating, roll brush coating, spray coating, dip roll coating, bar coating, and blade coating. Methods such as cloth, air knife coating, curtain coating, die lip coating, extrusion coating by die nozzle coater, etc.

The temperature of the heating and drying is preferably 40 to 200 ° C, more preferably 50 to 180 ° C, and particularly preferably 70 to 170 ° C. By setting the heating temperature to the above range, a resin layer having excellent adhesive properties can be obtained. The heating and drying time is preferably 5 seconds to 20 minutes, more preferably 5 seconds to 15 minutes, and even more preferably 10 seconds to 10 minutes.

In a state in which the (meth) acrylic polymer is produced by polymerizing a monomer component by ultraviolet irradiation, the (meth) acrylic polymer can be produced from the monomer component, and a resin layer can be formed. In the monomer component, materials such as a cross-linking agent that can be blended in the resin composition can be blended as appropriate. When the said monomer component can be used for ultraviolet irradiation, a part is polymerized beforehand, and it can be made into a syrup form. In the ultraviolet irradiation, a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or the like can be used.

Examples of the support include a polyolefin film containing polyolefin such as polyethylene (PE), polypropylene (PP), and ethylene-propylene copolymer as a main component, polyethylene terephthalate (PET), or In addition to polyester films such as polybutylene terephthalate as the main component, and polyvinyl chloride films based on polyvinyl chloride as the main component, polyether 碸 films, polystyrene films, Polyacrylic film, polyurethane film, polyimide film, polyimide film, polyimide film, cyclic olefin film, ethylene-vinyl alcohol copolymer film and other plastic films; paper, Porous materials such as cloth and non-woven fabrics; meshes; bubble-containing sheets such as polyethylene foam or acrylic foam; metal foils; and various supporting films such as composites. Examples of the composite include a laminated body of a metal foil and a plastic film, or a plastic film reinforced with an inorganic fiber such as glass fiber or carbon fiber, but are not limited thereto. The concept of bubbles in the bubble-containing sheet includes bubbles without a solid shell and bubbles with a solid shell (for example, those containing hollow particles). Therefore, in this application, the above-mentioned bubble-containing sheet may be described as "a sheet containing bubbles or particles". The air bubble or particle-containing sheet may include one or both of air bubbles without a solid shell and air bubbles with a solid shell.
The thickness of the supporting film is generally suitable to be about 5 μm to 3000 μm, and may be preferably 10 μm to 2500 μm, and more preferably 20 μm to 2000 μm. In some aspects, the thickness of the support film may be, for example, 1000 μm or less, 500 μm or less, 300 μm or less, or 100 μm or 50 μm or less.

If necessary, the above-mentioned support film may be subjected to a mold release and antifouling treatment with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid ammonium-based release agent or silicon dioxide powder. In addition, the support film may be subjected to an antistatic treatment such as coating, kneading, and vapor deposition with an antistatic agent.

A structural example of a laminated sheet according to an embodiment is schematically shown in FIG. 1. The laminated sheet 1 includes a support film 10 having a first surface 10A and a second surface 10B, and an adhesive layer 21 which is a resin layer provided on the first surface 10A side. The first surface 10A is non-peelable, whereby the laminated sheet 1 is configured as a single-sided adhesive sheet with a base material. As shown in FIG. 1, the laminated sheet 1 before use (that is, before being attached to the adherend) may further include a release liner 31 that protects the surface (adhesive surface) 21A of the adhesive layer 21. The release liner 31 is a release surface (release surface) on at least the side that is in contact with the adhesive surface 21A. In practice, the release liner 31 is peeled from the adhesive surface 21A.

A structural example of a laminated sheet according to another embodiment is schematically shown in FIG. 2. The laminated sheet 2 includes: a supporting film 10 having a first surface 10A and a second surface 10B; an adhesive layer 21 that is a resin layer provided on the first surface 10A side; and an adhesive layer 22 that is A resin layer provided on the second surface 10B side. Both the first surface 10A and the second surface 10B are non-peelable, whereby the laminated sheet 2 is configured as an adhesive sheet on both sides with a substrate. As shown in FIG. 2, the adhesive sheet 2 before use may further include a release liner 31 that protects the surface (first adhesive surface) 21A of the adhesive layer 21 and the surface (second adhesive surface) 22A of the adhesive layer 22, 32. The release liners 31 and 32 are at least the sides that come into contact with the adhesive surfaces 21A and 22A to become release surfaces. In practical use, the release liners 21 and 22A are peeled off.

A structural example of a laminated sheet according to still another embodiment is schematically shown in FIG. 3. The laminated sheet 3 includes: an adhesive layer 21 which is a resin layer; a release liner 31 which protects one surface (first adhesive surface) 21A of the adhesive layer 21; and a release liner 32 which protects the adhesive layer The other surface of 21 (the second adhesive surface) 21B. In practice, the release liners 31 and 32 are peeled from the adhesive surfaces 21A and 21B. The adhesive layer 21 of this embodiment can also be grasped as an adhesive sheet without a non-peelable support, that is, an adhesive sheet without a substrate.

Examples of constituent materials of the release liner include plastic films such as polyethylene, polypropylene, polyethylene terephthalate, and polyester films, porous materials such as paper, cloth, and non-woven fabrics, meshes, and air bubbles Suitable sheet materials such as sheets, metal foils, and the like are used. In terms of excellent surface smoothness, a plastic film can be preferably used.

The plastic film is not particularly limited as long as it can protect the resin layer, and examples thereof include polyethylene films, polypropylene films, polybutene films, polybutadiene films, and polymethylpentene films. , Polyvinyl chloride film, vinyl chloride copolymer film, polyethylene terephthalate film, polybutylene terephthalate film, polyurethane film, ethylene-vinyl acetate copolymer film, and the like.

The thickness of the release liner is usually 5 to 300 μm, and preferably about 5 to 200 μm. If necessary, the release liner may be subjected to a mold release, antifouling treatment, or coating with a silicone-based, fluorine-based, long-chain alkyl-based or fatty acid ammonium-based release agent, silicon dioxide powder, or the like. Type, mixed type, evaporation type and other anti-static treatment. In particular, by appropriately performing a release treatment such as a polysiloxane treatment, a long-chain alkyl treatment, or a fluorine treatment on the surface of the release liner, the releasability from the resin layer can be further improved.

The resin layer disclosed herein (can be a resin layer constituting an adhesive sheet without a substrate, a single-sided adhesive sheet with a substrate, or a resin layer with both surfaces of a substrate. The same applies hereinafter) with a polypropylene (PP) board The room-temperature 180 ° peeling adhesion force (hereinafter, also referred to as relative PP room-temperature adhesion force) measured as an adherend is preferably 10 N / 20 mm or more, and more preferably 11 N / 20 mm or more. The relative PP room temperature adhesion of the resin layer may be, for example, 12 N / 20 mm or more, and may also be 13 N / 20 mm or more. The upper limit of the room temperature adhesive force with respect to PP is not particularly limited, and may be, for example, about 30 N / 20 mm or less.

The resin layer disclosed herein preferably has a 180 ° peeling adhesion force (hereinafter, also referred to as relative room temperature adhesion force with respect to the plywood) measured at room temperature with a coniferous plywood as an adherend, which is 8 N / 20 mm or more. The above-mentioned plywood adhesive force at room temperature is more preferably 10 N / 20 mm or more, more preferably 15 N / 20 mm or more, and also 18 N / 20 mm or more or 20 N / 20 mm or more. There is no particular limitation on the upper limit of the room-temperature bonding force with respect to the plywood, and it may be, for example, about 50 N / 20 mm or less, or about 40 N / 20 mm or less.

The resin layer disclosed here is preferably a room-temperature 180 ° peeling adhesive force (hereinafter, also referred to as a relative calcium silicate plate room temperature adhesive force) measured using a calcium silicate plate as an adherend, which is 10 N / 20 mm or more. . The above-mentioned bonding force of the calcium silicate board at room temperature is more preferably 15 N / 20 mm or more, and may also be 20 N / 20 mm or more. The upper limit of the room temperature adhesion force relative to the calcium silicate board is not particularly limited, and may be, for example, about 50 N / 20 mm or less, or about 40 N / 20 mm or less.

In the resin layer disclosed herein, the low-temperature 180 ° peeling adhesive force (hereinafter, also referred to as low-temperature adhesive force with respect to the plywood) measured using a coniferous plywood as an adherend may be, for example, 1 N / 20 mm or more or 3 N / 20 mm or more, preferably 5 N / 20 mm or more. In some aspects, the low-temperature bonding force of the relative plywood may be, for example, 7 N / 20 mm or more, and may also be 9 N / 20 mm or more. Since the (meth) acrylic polymer is a polymer containing monomer components of the monomer A1 and the monomer A2 at a specific ratio, the polymer is also excellent in flexibility in a low temperature range. Therefore, even if a specific amount of the adhesion-imparting resin is blended with the (meth) acrylic polymer, the rough surface of the coniferous plywood and the like can exhibit good adhesion in a low temperature range, and the low temperature adhesion can be achieved better. force. The upper limit of the low-temperature bonding force to the plywood is not particularly limited, and may be, for example, about 50 N / 20 mm or less, or about 40 N / 20 mm or less.

The 180 ° peeling adhesive force at room temperature and the 180 ° peeling adhesive force at low temperature of the resin layer were measured by the methods described in the following examples. In the resin layer constituting the adhesive layer without a substrate (that is, the resin layer without a non-peelable support), when measuring the 180 ° peel adhesion, an appropriate liner can be attached to one side of the resin layer. Base material (such as a PET film with a thickness of about 25 μm). The same applies to the following holding force test. In addition, the same reinforcement can be applied to the resin layer constituting the single-sided adhesive sheet with the base material or the double-sided adhesive sheet with the base material as needed.

The offset distance in the retention force test of the resin layer disclosed here by the method described in the following examples is preferably less than 1.0 mm, and more preferably 0.8 mm or less. Such a laminated sheet-based resin layer has a moderately high cohesive force. According to this resin layer, the adherend can be firmly bonded or fixed.

＜ Applications ＞
The resin layer disclosed herein can be preferably used for attaching an adherend or a plastic having a rough surface. Examples of the adherend having a rough surface include concrete, mortar, gypsum board, coniferous board, wood-based cement board, calcium silicate board, tile, and fiber-reinforced cement board, but are not limited thereto. The arithmetic average roughness Ra of the rough surface may be, for example, about 1 μm to 800 μm. The laminated sheet is particularly preferably used for an adherend having a rough surface having an arithmetic average roughness Ra of 1 μm to 500 μm. The arithmetic average roughness Ra of the rough surface may be, for example, about 3 μm to 300 μm, or may be about 5 μm to 150 μm. In addition, the resin layer and the laminated sheet disclosed herein can be firmly adhered to a smooth adherend, and can also be preferably applied to such an adherend.

The resin layer disclosed herein can effectively utilize the characteristics that can be adhered to any of the rough surface and the plastic, and is preferably used for attaching to both the rough surface and the plastic (for example, Application of bonding body and plastic member). The plastic may be a low-polarity plastic such as a polyolefin resin such as PP or PE.

The matters disclosed in this manual include the following matters.
[1] A resin composition comprising a (meth) acrylic polymer having a glass transition temperature of -40 ° C or lower, and 5 parts by weight or more with respect to 100 parts by weight of the (meth) acrylic polymer. Those with a viscosity of 40 parts by weight or less, and the (meth) acrylic polymer is a homopolymer having a glass transition temperature of -50 ° C or lower and a branched alkane having 8 to 18 carbons at the end of the ester group (Meth) acrylic acid alkyl ester (A1) of 50 to 97% by weight, and (meth) acrylic acid ester (A2) having a glass transition temperature of -40 ° C or lower and having an ether bond in a molecular skeleton of a homopolymer 3 to 50% by weight
Polymer of monomeric ingredients.
[2] The resin composition according to the above [1], wherein a total ratio of the (meth) acrylic acid alkyl ester (A1) and the (meth) acrylic acid ester (A2) having an ether bond with respect to the above-mentioned ( All monomer components of the (meth) acrylic polymer are 75% by weight or more.
[3] The resin composition according to the above [1] or [2], wherein the (meth) acrylate (A2) having an ether bond is a monomer represented by the general formula (1):
CH ₂ = CR ¹ -COO- (AO) _n -R ²
(In the above general formula (1), R ¹ is a hydrogen atom or a methyl group, AO is an alkoxy group having 2 to 3 carbon atoms, and n is a number representing the average addition mole number of the alkoxy group and is 1 to 10, and R ² is an aromatic ring, or a linear, branched, or alicyclic alkyl group).
[4] The resin composition according to the above [3], wherein AO in the general formula (1) is an oxyethylene group.
[5] The resin composition according to the above [3] or [4], wherein n in the general formula (1) is 2 to 8.
[6] The resin composition according to any one of the above [3] to [5], wherein the carbon number of R ² in the general formula (1) is 1 to 6.
[7] The resin composition according to any one of the above [1] to [6], wherein the adhesion-imparting resin comprises a resin selected from a rosin-based adhesion-imparting resin, a terpene-based adhesion-imparting resin, a petroleum-based adhesion-imparting resin, and benzene At least one of a group consisting of vinyl-based adhesion-imparting resin.
[8] The resin composition according to any one of the above [1] to [7], which contains at least one adhesion-imparting resin having a softening point of 90 ° C. or higher and 160 ° C. or lower as the adhesion-imparting resin.
[9] The resin composition according to any one of the above [1] to [8], wherein the monomer component is selected from the group consisting of a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group. At least one functional group-containing monomer in the group.
[10] The resin composition according to any one of the above [1] to [9], wherein the monomer component further contains 5% by weight or less based on all the monomer components forming the (meth) acrylic polymer. Or 3% by weight or less of a polyfunctional monomer.
[11] The resin composition according to any one of the above [1] to [10], wherein the weight average molecular weight of the (meth) acrylic polymer is 350,000 or more.
[12] The resin composition according to any one of the above [1] to [11], which further contains 0.01 part by weight or more and 5 parts by weight or less based on 100 parts by weight of the (meth) acrylic polymer. Crosslinking agent.
[13] The resin composition according to the above [12], wherein the crosslinking agent includes one or both of an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent.
[14] A resin layer formed from the resin composition according to any one of the above [1] to [13].
[15] The resin layer according to the above [14], wherein the storage elastic modulus G ′ (23 ° C.) is 1.0 × 10 ⁴ Pa or more and 5.0 × 10 ⁴ Pa or less.
[16] The resin layer according to the above [14] or [15], wherein the storage elastic modulus G '(-10 ° C) is 3.0 × 10 ⁴ Pa or more and 7.0 × 10 ⁵ Pa or less.
[17] The resin layer according to any one of the above [14] to [16], wherein the polymer gel fraction is 20% by weight or more and 98% by weight or less.
[18] The resin layer according to any one of the above [14] to [16], wherein the polymer gel fraction is 20% by weight or more and 95% by weight or less.
[19] The resin layer according to any one of the above [14] to [18], wherein a haze value when the thickness of the resin layer is 85 μm is 1.9% or less.
[20] A laminated sheet comprising:
A support; and the resin layer as set forth in any one of [14] to [19] above, provided on at least one side of the support.
[21] The laminated sheet according to the above [20], wherein the 180 ° peeling adhesive force measured at 23 ° C and at a peeling speed of 300 mm / min is 10 N / 20 mm or more .
[22] The laminated sheet according to the above [20] or [21], wherein the 180 ° peeling adhesion force measured at a temperature of -10 ° C and a peeling speed of 300 mm / min is 5 N / 20 mm or more.
[23] The laminated sheet according to any one of the above [20] to [22], wherein the support includes at least any one of a plastic film, paper, non-woven fabric, and a sheet containing air bubbles or particles.
[24] The laminated sheet according to any one of the above [20] to [23], which is used by being attached to an adherend having a rough surface, the adherend being made of concrete, mortar, gypsum board, or conifer plywood , Wood cement board, calcium silicate board, tile and fiber reinforced cement board.
[25] The laminated sheet according to the above [24], which is used for joining the above-mentioned adherend having a rough surface to a plastic member.
[26] A laminated structure including an adherend having a rough surface and the resin layer according to any one of the above [14] to [19], wherein the resin layer is bonded to the rough surface through the resin layer, and The adherend is integrated with the resin layer.
[27] A laminated structure including an adherend having a rough surface and the laminated sheet according to any one of the above [20] to [23], and bonding the rough surface with the resin layer, The adherend is integrated with the laminated sheet.
[28] The laminated structure according to the above [26] or [27], wherein the adherend having a rough surface is made of concrete, mortar, gypsum board, coniferous wood board, wood cement board, calcium silicate board, tile And fiber reinforced cement board.
[Example]

Hereinafter, several embodiments related to the present invention will be described, but it is not intended to limit the present invention to those shown in such specific examples. In addition, "part" and "%" in the following description are based on weight unless otherwise specified.

Example 1
(Preparation of (meth) acrylic polymer)
90 parts of 2-ethylhexyl acrylate (2EHA), 10 parts of ethyl carbitol acrylate (CBA), 0.25 parts of 4-hydroxybutyl acrylate (4HBA), and 1 part of acrylic acid (AA) were used as polymerization initiation Add 0.1 parts of 2,2'-azobisisobutyronitrile (AIBN) and 160 parts of ethyl acetate to a four-necked flask equipped with a stirring wing, a thermometer, a nitrogen introduction tube, and a cooler, and introduce them while stirring slowly. After nitrogen was substituted for 1 hour, the temperature of the liquid in the flask was maintained at about 60 to 65 ° C. for 10 hours to perform a polymerization reaction to prepare a (meth) acrylic polymer solution. The Mw determined by GPC of the (meth) acrylic polymer was 850,000. The Tg of the (meth) acrylic polymer calculated from the monomer composition was -68.7 ° C.

Next, in the (meth) acrylic polymer solution obtained above, a polymerized rosin ester (manufactured by Arakawa Chemical Industries, Inc., trade name: PENSEL D125, which is an adhesive-imparting resin) was prepared based on 100 parts of the solid content of the polymer. , Softening point: 120 to 130 ° C) 20.0 parts, and 0.55 part of trimethylolpropane adduct of 2,4-toluene diisocyanate (manufactured by Tosoh Corporation, trade name: Coronate L) as a cross-linking agent to prepare a resin Composition solution.

This resin composition solution was applied to the release surface of a release liner so that the thickness of the dried resin layer became 85 μm, and dried at 130 ° C. for 3 minutes to form a resin layer. Thereby, a laminated sheet having a resin layer on one side of the release liner (that is, a release support) was obtained. As the above-mentioned release liner, a PET film (manufactured by Mitsubishi Resin Co., Ltd., DIAFOIL MRF) having a thickness of 38 μm on one side which became a release surface treated with polysiloxane was used. The above resin layer can also be grasped as an adhesive layer without a substrate.

Examples 2 to 16 and Comparative Examples 1 to 3
In Example 1, the types of monomers used in the preparation of the (meth) acrylic polymer and their composition ratios, the types of adhesion-imparting resins and their blending amounts, and the amounts of crosslinking agents were set as shown in Table 1. Except for the type and the blending amount thereof, a resin layer having a thickness of 85 μm was produced on the release surface of the release liner by the same operation as in Example 1 to obtain a laminated sheet. The Mw and Tg of the (meth) acrylic polymer of each example are shown in Table 1.

The following evaluation was performed about the resin layer which comprises the laminated sheet obtained by the said Example and the comparative example. The evaluation results are shown in Tables 1 and 2.

＜ Measurement of polymer gel fraction ＞
A specific amount (initial weight W1) of the sample was collected from the resin layer, immersed in an ethyl acetate solution, and left at room temperature for one week, and the insoluble matter was taken out to measure the weight (W2) after drying. Formula to calculate the gel fraction of the resin layer.
Gel fraction of resin layer (%) = (W2 / W1) × 100
From the obtained gel fraction of the resin layer, a polymer gel fraction was calculated by the following formula. The number of adhesion-imparting resins in the following formula means the number of adhesion-imparting resins contained in the resin layer relative to 100 parts of the polymer contained in the resin layer.
Polymer gel fraction (%) = resin layer gel fraction (%) × (100 + number of resins given by adhesion) / 100

<Measurement of storage elastic modulus G '>
A resin layer was laminated to produce a laminated body having a thickness of about 2 mm. The laminate was punched into a disc-shaped sample having a diameter of 7.9 mm by sandwiching a parallel plate, and the temperature dispersion measurement was performed using a viscoelasticity test device under the following conditions. From the results, the storage elastic modulus G '(unit; Pa) at 23 ° C and -10 ° C was read.
[Test conditions]
Device: ARES manufactured by TA Instruments
Deformation mode: Torsion measurement frequency: fixed frequency 1 Hz (strain: 0.1%)
Heating rate: 5 ° C / min Measurement temperature: Measurement from -70 ° C to 100 ° C Shape: Parallel plate with a diameter of 8.0 mm

<Measurement of room temperature adhesion>
A PET film (Lumirror S10, manufactured by Toray Industries, Inc.) with a thickness of 25 μm was attached to one surface of each of the resin layers as a substrate and used as a sample for evaluation. The evaluation sample was cut into a width of 20 mm and a length of about 100 mm to prepare a test piece. Then, in a standard environment of 23 ° C and 50% RH, the 2 kg roller was reciprocated once to attach the adhesive surface of the test piece (that is, the other side of the resin layer) to the coniferous wood plywood as the adherend (from Acquired by Shimachu Homes, thickness 12 mm), calcium silicate board (Stendo # 400 manufactured by A & A Material Co., Ltd., thickness 6 mm) or polypropylene board (Kobe Polysheet manufactured by Shin Kobe Electric Co., Ltd., thickness 2 mm). After leaving it to stand for 30 minutes in the standard environment described above, the peeling adhesion force (N / 20 mm) was measured under the same environment at a peeling angle of 180 ° and a peeling speed of 300 mm / min.

In a standard environment of 23 ° C and 50% RH, a 2 kg roller was reciprocated once to attach the adhesive surface of the test piece (that is, the other surface of the resin layer) to a glass plate (Songlang) as an adherend. (Manufactured by GLASS INDUSTRIAL CO., LTD., Thickness 1.2 mm). After leaving it to stand for 30 minutes in the standard environment described above, the peeling adhesion force (N / 20 mm) was measured under the same environment at a peeling angle of 180 ° and a peeling speed of 300 mm / min.

＜ Low temperature adhesive force measurement ＞
An evaluation sample prepared in the same manner as the above-mentioned room temperature adhesion measurement was cut into a width of 20 mm and a length of about 100 mm to prepare a test piece. Next, after the adherend and the evaluation sample were stored in an environment at -10 ° C for more than one hour, the 2 kg roller was reciprocated once under the same environment to attach the adhesive surface of the test piece as the adherend. Conifer Plywood (obtained from Shimachu Homes, thickness 12 mm). After this was left to stand in an environment at -10 ° C for 30 minutes, the peel adhesion force (N / 20 mm) was measured under the same environment at a peel angle of 180 ° and a peel speed of 300 mm / min.

＜ Retention force measurement ＞
An evaluation sample prepared in the same manner as the above-mentioned room temperature adhesion measurement was cut into a width of 10 mm and a length of about 100 mm to prepare a test piece. Next, with a bonding area of 10 mm in width and 20 mm in length, the 2 kg roller was reciprocated once to pressure-bond the adhesive surface of the test piece to a bake board (manufactured by Sumitomo Bakelite, thickness 2 mm). After the adherend with the test piece so attached was left to stand at room temperature (23 ° C) for 30 minutes, the test piece was suspended so that the longitudinal direction of the test piece became vertical, and 500 g of the free end of the test piece was given. After the load was left in an environment at 40 ° C for 1 hour, the offset distance (mm) from the initial attachment position of the test piece was measured.

＜ Haze value measurement ＞
A test piece prepared by attaching the resin layer of each example to a single surface of an alkali-free glass having a total light transmittance of 93.3% and a haze value of 0.1% was used as a test piece, and a haze meter (MR-100, Murakami Color Technology Research Institute) was used as a test piece. (Manufacturing) The haze value of this test piece was measured. During the measurement, the test piece was arranged so that the resin layer was on the light source side. Since the haze value of the alkali-free glass is 0.1%, the value obtained by subtracting 0.1% from the measured value is taken as the haze value of the resin layer.

[Table 1]

[Table 2]

The meanings of the abbreviations used in Table 1 are as follows.
2EHA: 2-ethylhexyl acrylate (manufactured by Toa Kosei, Tg of homopolymer = -70 ° C).
CBA: ethyl carbitol acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg of homopolymer = -67 ° C).
MTG: methoxytriethylene glycol acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg of homopolymer = -57 ° C).
4HBA: 4-hydroxybutyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd., Tg of homopolymer = -32 ° C).
AA: acrylic acid (manufactured by Toa Kosei Co., Ltd., Tg of homopolymer: 106 ° C).
BA: Butyl acrylate (manufactured by Toa Synthesis Co., Ltd., Tg of homopolymer = -55 ° C).
C: Trimethylolpropane / 2,4-toluene diisocyanate terpolymer adduct (manufactured by Tosoh Corporation, trade name: Coronate L).
DN: Trimethylolpropane adduct of xylylene diisocyanate (manufactured by Mitsui Chemicals, trade name: Takenate D110N)
D: Polymerized rosin ester with a softening point of 120 to 130 ° C (manufactured by Arakawa Chemical Industries, Ltd., trade name: PENSEL D125).
A: Rosin ester with a softening point of 95 to 105 ° C (manufactured by Arakawa Chemical Industries, Ltd., trade name: PENSEL AZ).
T: terpene phenol resin with a softening point of 125 to 135 ° C (manufactured by Yasuhara Chemical Co., Ltd., trade name: YS Polyster T130)
ND: Not evaluated.

As shown in Table 2, the resin layer formed from the resin compositions of Examples 1 to 16 exhibited a high room-temperature adhesion to both the rough surface and the plastic, and showed good adhesion to the rough surface even at low temperatures. Sex. These resin layers are also excellent in retention.

The specific examples of the present invention have been described in detail above, but these are merely examples and do not limit the scope of patent application. The technology described in the patent application scope includes various changes and modifications to the specific examples illustrated above.

1‧‧‧ laminated sheet

2‧‧‧ laminated sheet

3‧‧‧ laminated sheet

10‧‧‧ support film (support body)

10A‧‧‧First side

10B‧‧‧Second Side

21‧‧‧Adhesive layer (resin layer)

21A‧‧‧ Adhesive surface (first adhesive surface)

21B‧‧‧ Adhesive surface (second adhesive surface)

22‧‧‧Adhesive layer (resin layer)

22A‧‧‧ Adhesive surface (second adhesive surface)

31‧‧‧ Release liner

32‧‧‧ Release liner

FIG. 1 is a cross-sectional view schematically showing the configuration of a laminated sheet according to an embodiment.

FIG. 2 is a cross-sectional view schematically showing the structure of a laminated sheet according to another embodiment.

FIG. 3 is a cross-sectional view schematically showing the configuration of a laminated sheet according to still another embodiment.

Claims (17)

A resin composition containing a (meth) acrylic polymer having a glass transition temperature of -40 ° C or lower, and 5 to 40 parts by weight or more of the (meth) acrylic polymer-based adhesive-imparting resin, and The (meth) acrylic polymer-based (Meth) acrylic acid alkyl ester (A1) having a glass transition temperature of -50 ° C or lower and having a branched alkyl group having 8 to 18 carbon atoms at the end of the ester group, 50 to 97% by weight, and (Meth) acrylate (A2) having a glass transition temperature of -40 ° C or lower and having an ether bond in the molecular skeleton Polymer of monomeric ingredients. The resin composition according to claim 1, wherein the total ratio of the (meth) acrylic acid alkyl ester (A1) to the (meth) acrylic acid ester (A2) having an ether bond is relative to the formation of the (meth) acrylic acid All monomer components of the polymer are 75% by weight or more. The resin composition according to claim 1 or 2, wherein the (meth) acrylate (A2) having an ether bond is a monomer represented by the general formula (1): CH ₂ = CR ¹ -COO- (AO) _n -R ² (In the above general formula (1), R ¹ is a hydrogen atom or a methyl group, AO is an alkoxy group having 2 to 3 carbon atoms, and n is an average addition mole number of the above alkoxy group. The number is 1 to 10, and R ² is an aromatic ring, or a linear, branched, or alicyclic alkyl group). The resin composition according to any one of claims 1 to 3, wherein the adhesion-imparting resin comprises a resin selected from the group consisting of a rosin-based adhesion-imparting resin, a terpene-based adhesion-imparting resin, a petroleum-based adhesion-imparting resin, and a styrene-based adhesion-imparting resin. At least one of the group. The resin composition according to any one of claims 1 to 4, comprising as the above-mentioned adhesion-imparting resin at least one adhesion-imparting resin having a softening point of 90 ° C or higher and 160 ° C or lower. The resin composition according to any one of claims 1 to 5, wherein the above-mentioned monomer component comprises at least one selected from the group consisting of a monomer having a hydroxyl group, a monomer having a carboxyl group, and a monomer having an epoxy group. Functional group-containing monomer. The resin composition according to any one of claims 1 to 6, wherein the weight average molecular weight of the (meth) acrylic polymer is 350,000 or more. The resin composition according to any one of claims 1 to 7, further comprising a crosslinking agent in an amount of 0.01 to 5 parts by weight based on 100 parts by weight of the (meth) acrylic polymer. The resin composition according to claim 8, wherein the crosslinking agent comprises one or both of an isocyanate-based crosslinking agent and an epoxy-based crosslinking agent. A resin layer formed from the resin composition according to any one of claims 1 to 9. If the resin layer of claim 10 has a storage elastic modulus G 'at 23 ° C of 1.0 × 10 ⁴ Pa or more and 5.0 × 10 ⁴ Pa or less, and a storage elastic modulus G' at -10 ° C of 3.0 × 10 ⁴ Pa or more and 7.0 × 10 ⁵ Pa or less. For example, the resin layer of claim 11 has a polymer gel fraction of 20% by weight to 95% by weight. The resin layer according to any one of claims 10 to 12, wherein the haze value when the thickness of the resin layer is 85 μm is 1.9% or less. A laminated sheet comprising: Support; and The resin layer according to any one of claims 10 to 13 provided on at least one side of the support. For example, the laminated sheet of claim 14, wherein the 180 ° peeling adhesive force measured at a peeling speed of 300 mm / min under the environment of the above-mentioned resin layer is 10 N / 20 mm or more. For example, the laminated sheet of claim 14 or 15, wherein the 180 ° peeling adhesive force measured at a peeling speed of 300 mm / min under the environment of -10 ° C is 5 N / 20 mm or more. The laminated sheet according to any one of claims 14 to 16, wherein the support comprises at least any one of a plastic film, paper, non-woven fabric, and a sheet containing air bubbles or particles.