JP5737512B2 - Adhesive composition, adhesive sheet, and laminate - Google Patents

Description

  The present invention provides a curable adhesive composition, an adhesive sheet using the same, and a laminate obtained by laminating the adhesive sheet.

  Conventionally, as a method for decorating a molded object to be decorated, for example, painting, a method by application of a clear coat agent, etc., decorating with a decorative label or various decoration sheets has been performed. . Methods such as painting and application of clear coat agents have the problem of environmental degradation due to the use of solvents, and the method of attaching decorative labels and metal vapor-deposited sheets is only partially applied to molded products with complex shapes. There were problems such as inability to decorate.

In order to solve this problem, there is a demand for a method that does not depend on coating. For example, various types of integrated molding such as vacuum molding have been proposed and are widely used for display boards of home appliances, interiors of cars, and the like.
However, when an adhesive made of a thermoplastic resin is used for integral molding, the adhesive becomes plastic at high temperatures and the adhesive strength decreases. Could not be applied. There is also a problem that the adhesive strength of the thermoplastic resin itself is originally low. On the other hand, when a thermosetting resin is used for integral molding, it must be cured at a high temperature for a long time. Therefore, the thermosetting resin and a molded body formed of a resin having low heat resistance are bonded. In the case of forming, the molded body has a problem of being deformed by heat.
In addition, when using ionizing radiation curable resin that is instantly cured by irradiation with ionizing radiation, etc., it is necessary to irradiate ionizing radiation after lamination, and a material that can transmit ionizing radiation through either an article or another article There was a problem that had to be made.

Patent Document 1 discloses an active energy ray-curable colored coating composition for a vacuum molded film, a vacuum molded film obtained from the composition, and a vacuum molded product obtained by laminating the film. The vacuum molded film itself is easy to handle because it is not tacky, and is instantly bonded to the molding material due to the heat softening property of the film. Furthermore, since the film is cured by active energy rays, it is vacuum molded in a short time. You can shape things.
Patent Document 2 discloses an adhesive transfer sheet in which an ionizing radiation curable adhesive layer is formed on a base sheet, and the article and other articles even after the ionizing radiation adhesive layer is irradiated with ionizing radiation. And an adhesive transfer sheet that has a higher adhesive strength between the article and the other article after the lapse of a certain time from the temporary adhesion than the adhesive strength between the article and the other article at the time of temporary adhesion. It is disclosed. However, the integrally formed product by vacuum forming disclosed in Patent Document 2 needs to be irradiated with ionizing radiation after lamination.

  Patent Document 3 discloses a molded sheet for decorating a molded product used for decorating the surface of a decorated molded product, and an adhesive used for the molded sheet. The decorative molded sheet is composed of a thermoformable transparent plastic film such as an acrylic resin, a polycarbonate resin, and a polyester resin, a decorative layer, an adhesive layer, and the like. The adhesive that forms the adhesive layer is Since an acrylic resin, a urethane resin, a urethane-modified polyester resin, a polyester resin, or the like having a softening point in the range of 80 to 180 ° C. is used, there is a problem in that the adhesive becomes a plastic state at a high temperature and the adhesive strength is lowered. .

JP-A-6-100640 JP 2004-175863 A JP 2007-70518 A

  The present invention solves the above-mentioned conventional problems, has an appropriate viscoelasticity before curing, can be pressure-bonded with a weak pressure, does not need to be cured at a high temperature for a long time, and after curing It is an object of the present invention to provide a curable adhesive composition having high cohesive force, a sheet using the same, and a laminate obtained by laminating the adhesive sheet.

  The present invention has been made against the background of the above circumstances, a thermoplastic resin composed of an aliphatic polyamide resin that exhibits adhesiveness upon heating, a curing component composed of an epoxy resin, a thiol-based curing agent that exhibits flexibility, and ions The present inventors have found that the above problems can be solved by an adhesive composition containing a functional liquid, and have completed the present invention.

That is, the gist of the present invention is the invention described in the following (1) to (6).
(1) Epoxy resin (A) having two or more epoxy groups in one molecule, thermoplastic aliphatic polyamide (B), thiol compound (C) having two or more mercapto groups, and ionic liquid (D) only containing the thiol compound (C)
(I) a polythiol having a triazine skeleton,
(Ii) a thiol compound obtained by an esterification reaction of a polyol and a mercapto organic acid,
(Iii) an alkyl polythiol compound, and
(Iv) a terminal thiol group-containing polyether,
1 or 2 types or more selected from these, The adhesive composition characterized by the above-mentioned .
(2) The adhesive composition is formulated such that the active hydrogen equivalent of 0.7 to 1.2 equivalents of the thiol compound (C) with respect to 1 epoxy equivalent of the epoxy resin (A), and 1-10 mass parts of ionic liquids (D) are mix | blended with respect to 100 mass parts of thiol compounds (C), The adhesive composition as described in said (1) characterized by the above-mentioned.
(3) The polythiol having the triazine skeleton is 2,4,6-trimercapto-1,3,5-triazine,
1-hexylamino-3,5-dimercaptotriazine,
1-diethylamino-3,5-dimercaptotriazine,
1-cyclohexylamino-3,5-dimercaptotriazine,
1-dibutylamino-3,5-dimercaptotriazine,
(1) or (2) above, characterized in that it is one or more selected from 2-anilide-4,6-mercaptotriazine and 1-phenylamino-3,5-dimercaptotriazine The adhesive composition as described.

( 4 ) Epoxy resin (A) having two or more epoxy groups in one molecule, thermoplastic aliphatic polyamide (B), thiol compound (C) having two or more mercapto groups, and ionic liquid (D) possess adhesive composition the adhesive layer consisting of (H) (G) and the layer of one side or both sides peelable protective film layer (P) containing the thiol compound (C)
(I) a polythiol having a triazine skeleton,
(Ii) a thiol compound obtained by an esterification reaction of a polyol and a mercapto organic acid,
(Iii) an alkyl polythiol compound, and
(Iv) a terminal thiol group-containing polyether,
1 or 2 or more types selected from these, The adhesive sheet characterized by the above-mentioned .
( 5 ) An epoxy resin (A) having two or more epoxy groups in one molecule, a thermoplastic aliphatic polyamide (B), and two mercapto groups on a planar or three-dimensional object as an adherend. An adhesive layer (G) composed of an adhesive composition (H) containing at least one thiol compound (C) and an ionic liquid (D) is laminated, and the adhesive layer (G) In a state where at least one resin layer (M) is laminated thereon, the thiol compound (C) is heated and cured.
(I) a polythiol having a triazine skeleton,
(Ii) a thiol compound obtained by an esterification reaction of a polyol and a mercapto organic acid,
(Iii) an alkyl polythiol compound, and
(Iv) a terminal thiol group-containing polyether,
1 type or 2 types or more selected from these, The laminated body characterized by the above-mentioned .

Since the visco-adhesive composition of the present invention has an appropriate viscoelasticity before curing, it can be pressure-bonded with a weak pressure and exhibits a high cohesive force without being reacted for a long time at a high temperature. It can be applied regardless of the material to be worn. In addition, it is excellent in sheeting.
In addition, in the form of release separator / adhesive layer / release separator, the sheet suitability can be applied directly to the separator without problems such as repellency, and is adhesive when used (when the release separator is peeled off). It means that the release separator can be peeled off without causing cohesive failure of the layer.
And since the adhesive sheet which has an adhesive layer which consists of such an adhesive composition of this invention has moderate adhesiveness and favorable adhesiveness, the improvement of the physical property of a laminated body It is useful for imparting functionality. Moreover, it is excellent in moldability and can be suitably used particularly for an integral molding method by vacuum formation. Furthermore, the laminate obtained by laminating the adhesive sheet is also excellent in design, mechanical strength, and durability.

An example of the formation example of the molded object using the laminated body of this invention is shown. The other example of the formation example of the molded object using the laminated body of this invention is shown.

Hereinafter, (1) adhesive composition (H) (first aspect), (2) adhesive sheet (S) (second aspect), and (3) laminate (L) of the present invention. The (third aspect) will be described.
(1) Adhesive composition (H) (first embodiment)
The “adhesive composition (H)” (hereinafter sometimes referred to as an adhesive composition (H)), which is the first aspect of the present invention, has two or more epoxy groups in one molecule. The epoxy resin (A) has a thermoplastic aliphatic polyamide (B), a thiol compound (C) having two or more mercapto groups, and an ionic liquid (D).

  According to the adhesive composition (H) of the present invention, any adhesive material can be applied. In addition, it is excellent in sheeting. Furthermore, since it has moderate viscoelasticity before curing, it can be pressure-bonded with a weak pressure, and when it cures, it exhibits high cohesion without reacting at high temperature for a long time. Can be suitably used for the integral molding method. And the adhesive agent layer which consists of a thermosetting adhesive agent composition (H) shows favorable adhesiveness and adhesiveness with respect to a to-be-adhered body, and is excellent in durability. Hereinafter, each component contained in the adhesive composition (H) will be specifically described.

(1-1) Epoxy resin (A)
The epoxy resin (A) blended in the adhesive composition (H) of the present invention is an epoxy resin having two or more epoxy groups in one molecule, such as bisphenol type, ether ester type, novolac epoxy. Molds, ester types, aliphatic types, and other known modified epoxy resins can be used. In the adhesive composition (H) of the present invention, an epoxy resin having two epoxy groups in one molecule is preferable in order to satisfy both storage stability and curability, but one in one molecule. It is possible to mix the epoxy resin having an epoxy group in an amount not exceeding 10 mol% in the epoxy resin (A). The higher the epoxy group concentration in the molecule (the lower the epoxy equivalent), the higher the reaction probability with the curing agent, generally the faster the reaction rate, and the higher the epoxy group concentration, the higher the glass transition temperature. In consideration of storage stability and reactivity and short-time curability, the epoxy resin (A) may contain 50 mol% or more of an epoxy resin having two or more epoxy groups in one molecule. Preferably, 70 mol% or more is contained, more preferably 80 mol% or more.

  Moreover, the epoxy equivalent of an epoxy resin (A) is 100-800 g / eq. It is preferable to be within the range. The epoxy equivalent is the number of grams of resin containing 1 gram equivalent of an epoxy group measured by a method according to JIS K7236. Moreover, the mass average molecular weight of an epoxy resin (A) is not specifically limited, What is necessary is just to select suitably according to a use, However, Preferably it exists in the range of 300-2000. And in order to improve the adhesive force, durability, etc. of the adhesive agent layer formed, it is more preferable to use a high molecular weight within the above range. The epoxy resin (A) can be used in a solid or liquid state.

The epoxy resin (A) reacts with the epoxy resin with a relatively high molecular weight resin having an epoxy group at the terminal as an epoxy resin other than the above (hereinafter sometimes referred to as an epoxy resin (R)), A phenoxy resin that can be used as a thermosetting resin can be blended. Examples of the phenoxy resin include a phenoxy resin having a bisphenol A skeleton, a phenoxy resin having a bisphenol F skeleton, a phenoxy resin having a bisphenol S skeleton, and a bisphenol M skeleton (4,4 ′-(1,3-phenylenediisopridiene)). Phenoxy resin having bisphenol skeleton), phenoxy resin having bisphenol P (4,4 ′-(1,4) -phenylenediisopridiene) bisphenol skeleton) skeleton, bisphenol Z (4,4′-cyclohexyldiene bisphenol skeleton) ) Phenoxy resin having a bisphenol skeleton, phenoxy resin having a novolak skeleton, phenoxy resin having an anthracene skeleton, phenoxy resin having a fluorene skeleton, dicyclopentadiene skeleton Phenoxy resins having, phenoxy resins having a norbornene skeleton, phenoxy resins having a naphthalene skeleton, phenoxy resins having a biphenyl skeleton include a phenoxy resin having an adamantane skeleton. The molecular weight of the phenoxy resin is not particularly limited, but the weight average molecular weight is preferably 5,000 to 100,000. More preferably, it is 10000-70000. If a weight average molecular weight is more than the said lower limit, the effect which improves film forming property can fully be acquired. On the other hand, if it is below the said upper limit, solubility can be maintained and it is suitable.
An epoxy resin (R) can be mix | blended in the ratio of 30 mass parts or less with respect to 100 mass parts of epoxy resins (A) in an adhesive composition (H).

(1-2) Thermoplastic aliphatic polyamide (B)
The adhesive composition (H) of the present invention contains a thermoplastic aliphatic polyamide (B) (hereinafter, sometimes referred to as aliphatic polyamide (B). The adhesive composition (H) of the present invention. According to the present invention, since it contains the thermoplastic aliphatic polyamide (B), it can be pressure-bonded to a product decorating a decorative film or the like with a weak pressure. The polyamide (B) is not particularly limited, and examples thereof include aliphatic nylon and copolymers thereof, specifically, polycaproamide (nylon-6), polyaminoundecanoic acid (nylon-11). , Polylauryl lactam (nylon-12), polyhexamethylenediaminoadipic acid (nylon-66), polyhexamethylenediamino sebacic acid (nylon-610), polyhexamethylene Aminododecanedioic acid (nylon-612), caprolactam / lauryl lactam copolymer (nylon-6 / 12), caprolactam / aminoundecanoic acid copolymer (nylon-6 / 11), caprolactam / hexamethylenediaminoadipic acid copolymer Combined (nylon-6 / 66), caprolactam / hexamethylenediaminoadipic acid / aminododecanedioic acid (nylon-6 / 66/12), caprolactam / hexamethylenediaminoadipic acid / lauryllactam (nylon-6 / 66/12) Caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminosebacic acid (nylon-6 / 66/610), caprolactam / hexamethylenediaminoadipic acid / hexamethylenediaminododecanedioic acid (nylon-6 / 66 / 12), and the like. These may be used alone or in combination.

  As the aliphatic polyamide (B), for example, those having a mass average molecular weight in the range of 1000 to 200,000 are suitable, and the adhesive strength and durability of the formed adhesive layer are improved. It is preferable to use a high molecular weight within the above range. If the mass average molecular weight of the thermoplastic aliphatic polyamide (B) is less than 1000, the cohesive force of the cured adhesive layer is not sufficient, and durability may be inferior. Moreover, when it exceeds 200,000, sufficient initial adhesive force may not be obtained. The mass average molecular weight is determined by gel permeation chromatography (GPC) (column: manufactured by Tosoh Corporation, model: TSKgel αM, measurement temperature: 40 ° C., flow rate: 0.5 mL / min, solvent: tetrahydrofuran, standard substance: It is a value in terms of polystyrene when measured using polystyrene.

As a commercial item of the said aliphatic polyamide (B), TPAE-826-4S (made by Fuji Chemical Industry Co., Ltd.), TAPE-826-5A (made by Fuji Chemical Industry Co., Ltd.), Newmide 515-ME, for example. (Harima Kasei Co., Ltd.), Newmide 945 (Harima Kasei Co., Ltd.), Newmide 947 (Harima Kasei Co., Ltd.), etc. are suitable.
The content (in terms of solid content) of the aliphatic polyamide (B) in the adhesive composition (H) of the present invention is preferably 10 to 50% by mass. If the content of the thermoplastic aliphatic polyamide (B) is less than the lower limit of the above range, the cohesive force of the adhesive layer before curing is not sufficient, and sheeting may be difficult. Moreover, when the upper limit of the said range is exceeded, sufficient adhesive strength may not be obtained. From this viewpoint, the content (in terms of solid content) of the aliphatic polyamide (B) in the adhesive composition (H) is more preferably 15 to 40% by mass, and 15 to 30% by mass. Is more preferable.

(1-3) Thiol compound (C) having two or more mercapto groups
The adhesive composition (H) of the present invention contains a thiol compound (C) having two or more mercapto groups as a curing agent. The thiol compound (C) may be solid or liquid at room temperature. The solid state means a solid state at room temperature or the like excluding the heating temperature condition when the epoxy resin (A) is cured.
When the thiol compound (C) having two or more solid mercapto groups is used as a curing agent such as an epoxy resin (A), the storage stability is relatively good, but curing at a high temperature is required. was there.
In the present invention, the adhesive composition (H) in which the ionic liquid (D) is further blended with the thiol compound (C), which is the epoxy resin (A) and the curing agent, is curable without being heated to a high temperature. The reason why it is excellent is not clear, but the ionic liquid (D) having compatibility with various materials functions as a so-called compatibilizer with respect to the thiol compound (C). It is presumed that the thiol compound (C) will act as a curing agent without heating the product (H) to a high temperature. In addition, although the said expression is said, the said effect is acquired, when melting | fusing point falls, when an ionic liquid (D) is added to a thiol compound (C) using a differential thermal measuring apparatus, the said expression of compatibility is confirmed. it can.
As for the compounding quantity of the thiol compound (C) as a hardening | curing agent in the adhesive composition (H) of this invention, the active hydrogen equivalent is 0.7-1 with respect to 1 epoxy equivalent of an epoxy resin (A). It is preferable to mix | blend so that it may become 2 equivalent. The blending amount of the thiol compound (C) is 0.7 equivalent or more, and the effect that the curability is good even at a relatively low temperature and the adhesive strength after curing is remarkably exhibited. On the other hand, when the blending amount of the thiol compound (C) exceeds 1.2 equivalents, there is a risk that the initial tackiness and adhesiveness are lowered and the cost is increased.

Examples of the thiol compound (C) having two or more mercapto groups include the thiol compounds shown in the following (i) to (iv), but the thiol compound (C) of the present invention is not limited to these compounds. Absent.
(I) a polythiol having a triazine skeleton (ii) a thiol compound obtained by an esterification reaction of a polyol and a mercapto organic acid,
(Iii) alkyl polythiol compound,
(Iv) a terminal thiol group-containing polyether,

但し、式（１）中、Ｒ_１は水素原子、又は炭素原子数１〜５のアルキル基から選ばれる基を示す。

但し、式（２）中、Ｒ_２、Ｒ_３は、炭素原子数１〜５のアルキル基からそれぞれ独立に選ばれる基を示し、Ｒ_２、Ｒ_３は、同一であっても、異なっていてもよい。 Examples of the “(i) polythiol having a triazine skeleton” include polythiols represented by the following general formulas (1) and (2) having a triazine skeleton and having two or more mercapto groups.

In the formula (1), R ₁ represents a hydrogen atom, or a group selected from alkyl group having 1 to 5 carbon atoms.

However, in Formula (2), R < ₂ >, R < ₃ > shows group respectively independently selected from a C1-C5 alkyl group, R < ₂ >, R < ₃ > is the same, but is different. Also good.

In the solid triazine derivatives of the above general formulas (1) and (2), since at least two thiol groups are present, the reaction with the epoxy resin (A) having two or more epoxy groups in one molecule; Upon curing, a polymer epoxy resin is easily formed. Since R ₁ in the solid triazine derivative of the general formula (1) is a group selected from a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, the physical properties are similar to each other, and the ionic liquid (D ) And reactivity with the epoxy resin (A).
Examples of the alkyl group having 1 to 5 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, and pentyl group.
In the solid triazine derivative of the general formula (2), R ₂ and R ₃ each independently represents a group selected from an alkyl group having 1 to 5 carbon atoms, and R ₂ and R ₃ are the same. It may or may not be.
Since R ₂ and R ₃ are groups selected from alkyl groups having 1 to 5 carbon atoms, their physical properties are similar to each other, compatibility with the ionic liquid (D), and epoxy resin ( It will have reactivity with A). Specific examples of the alkyl group having 1 to 5 carbon atoms of R ₂ and R ₃ are the same as those described for the alkyl group of R ₁ .

Examples of the polythiol having a triazine skeleton represented by the general formulas (1) and (2) include the following polythiols.
2,4,6-trimercapto-1,3,5-triazine (also known as thiocyanuric acid),
1-hexylamino-3,5-dimercaptotriazine,
1-diethylamino-3,5-dimercaptotriazine,
1-cyclohexylamino-3,5-dimercaptotriazine,
1-dibutylamino-3,5-dimercaptotriazine,
2-anilide-4,6-mercaptotriazine,
And 1-phenylamino-3,5-dimercaptotriazine

Examples of (ii) “thiol compound obtained by esterification reaction of polyol and mercapto organic acid” include trimethylolpropane tris (thioglycolate), pentaerythritol tetrakis (thioglycolate), ethylene glycol dithioglycolate, trimethylol Examples include propanetris (β-thiopropionate), pentaerythritol tetrakis (β-thiopropionate), dipentaerythritol poly (β-thiopropionate), and the like.
Examples of the (iii) “alkyl polythiol compound” include 1,4-butanedithiol, 1,6-hexanedithiol, 1,10-decanedithiol, and the like.
(Iv) Examples of the “terminal thiol group-containing polyether” include Toray Fine Chemical Co., Ltd., Thiocol LP-2, LP-3 and the like.
In addition, as the thiol compound (C) of the present invention, in addition to those listed in (i) to (iv) above, (v) a terminal thiol group-containing polythioether, (vi) a thiol obtained by reacting an epoxy compound with hydrogen sulfide It is possible to use a compound, (vii) a thiol compound having a terminal thiol group obtained by a reaction between a polythiol and an epoxy compound.

(1-4) Ionic liquid (D)
“Salts” are usually fixed at room temperature like salt, but if the ions that make up the salt are replaced with relatively large (bulky) organic ions, the melting point will drop, and the liquid state will remain at room temperature. And such salts are called ionic liquids. In general, the ionic liquid maintains a liquid state even in a temperature range of −30 ° C. to + 300 ° C., and the vapor pressure is extremely low. Moreover, the ionic liquid is generally non-volatile and has a low viscosity.
Examples of the cation of the ionic liquid (D) used in the present invention include ammonium-based and phosphonium-based ions such as imidazolium salts and pyridinium salts. Examples of anions include halogens such as trifluorosulfonic acid (—CF ₃ SO ₂ ) and triflate (—SO ₃ CF ₃ ), phosphorus compounds such as hexafluorophosphate (—PF ₆ ), and tetraphenylborate. And boron-based materials.

As the cation of the ionic liquid (D) of the present invention, ammonium compounds such as imidazolium salts and pyridinium salts are preferable among the above examples. Examples of the anion include trifluorosulfonic acid (—CF ₃ SO ₂ ), triflate. Halogen type such as (—SO ₃ CF ₃ ) and phosphorus type such as hexafluorophosphate (—PF ₆ ) are preferable.
It is preferable that the compounding quantity of the ionic liquid (D) in the adhesive composition (H) of this invention is 1-10 mass parts with respect to 100 mass parts of thiol compounds (C).
The effect that the blending amount of the ionic liquid (D) is 1 part by mass or more, the curability is good even at a relatively low temperature, and the adhesive strength after curing is remarkable. On the other hand, when the blending amount of the ionic liquid (D) exceeds 10 parts by mass, there is a risk that dripping may occur at the time of curing due to the plasticizing action, or the cost may increase.

(1-5) Curing accelerator (E)
In this invention, a hardening accelerator (E) can be used as needed. Examples of the curing accelerator (E) include imidazole, amines, and phosphorus compound curing accelerators. Examples of the imidazole curing accelerator include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, 1 -Benzyl-2-phenylimidazole, 1-benzyl-2-methylimidazole, 2-phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole and the like.

  As amines, epoxy adduct tertiary amine (commercial product: Ajinomoto Fine-Techno Co., Ltd., trade name: ajicure MY-H), aromatic amine (commercial product: Asahi Kasei E-Materials Co., Ltd., trade name) : Novacure 3721), aliphatic polyamine (commercially available product: manufactured by Fuji Kasei Kogyo Co., Ltd., trade name: Fujicaer 1030), and the like. Examples of phosphorus compounds include triphenylphosphine, tri-o-tolylphosphine, tri-n-butylphosphine, and triphenylphosphite.

  Usually, the usage-amount of the hardening accelerator (E) which can be used for the adhesive composition (H) of this invention is 0.1 thru | or 10 mass parts with respect to 100 mass parts of epoxy resins (A). When the use amount of the curing accelerator is at least the lower limit of the above range, the crosslinking reaction is likely to proceed, and when it is below the upper limit of the above range, there is a possibility of suppressing the deterioration with time and stability against yellowing during curing.

(1-6) Curing retarder The curing retarder can be used as necessary to increase the pot life until the adhesive composition (H) is gelled. By including a curing retarder, the resulting adhesive composition (H) has a longer pot life and improved applicability. The curing retarder is not particularly limited. For example, a polyether compound such as polyethylene glycol, polypropylene glycol, polytetramethylene glycol, salicylic acid, oxalic acid, terephthalic acid, phosphoric acid, lactic acid, toluenesulfonic acid, boric acid ester The amount used is preferably 0.1 to 10 molar equivalents, more preferably 0.5 to 5 molar equivalents based on the molar equivalents of the thiol compound (C) that is the curing agent.

(1-7) Solvent (F)
Although it does not specifically limit as a solvent (F), For example, toluene, methyl ethyl ketone (MEK), ethyl acetate, dimethylacetamide, N-methyl-2-pyrrolidone, etc., these mixed solutions etc. are suitable as a dilution solvent. Can be used for Moreover, the usage-amount of a solvent (F) is not specifically limited, What is necessary is just to set suitably according to the coating method. However, from the viewpoint of the residual solvent amount, the solvent (F) is preferably blended in the adhesive composition (H) so as to be 10 to 70% by mass.

(1-8) Other resin The adhesive composition (H) of the present invention may contain a polyimide resin which is a thermosetting resin. By incorporating a resin such as a polyimide resin into the adhesive composition (H) of the present invention, it is possible to improve sheet forming ability and impart fine tack (tackiness) by imparting cohesive force before curing. Therefore, temporary fixing to various adherends becomes easy.
In order to obtain the above curing, a resin such as a polyimide resin is preferably in a liquid state, and a weight average molecular weight is preferably in the range of 10,000 to 500,000, and is used for an adhesive sheet (S) described later. In consideration of the case, the glass transition temperature is preferably 20 ° C. or lower in order to improve flexibility.

(1-9) Other components Various additives can be mix | blended with the adhesive composition (H) of this invention as needed in the range which does not impair the objective of this invention. For example, a coupling agent can be blended to improve adhesiveness and adhesion, and a crosslinking agent can be blended to adjust the tackiness. Furthermore, antioxidants, pigments, dyes, charging Various additives such as an inhibitor can be blended.

(1-10) Characteristics of the adhesive composition (H) (i) Tackiness The adhesive composition (H) of the present invention is excellent in tackiness.
When the adhesive composition (H) of the present invention forms an adhesive layer having a thickness of 15 μm, the adhesive layer peels off from the stainless steel plate by 180 ° (adhering to JIS Z0237). However, it is preferable that it is 0.5-20N / 25mm before hardening. If the adhesion before curing is less than 0.5 N / 25 mm, the initial adhesion may be inferior depending on the adherend, and if it exceeds 20 N / 25 mm, the initial adhesion is strong, so depending on the adherend Workability and removability may be inferior.
(B) Curability The adhesive composition (H) of the present invention is excellent in curability. The effectiveness of the composition (H) can be evaluated by the differential scanning calorimetry (DSC) based on the temperature of the exothermic peak and the calorific value at the time of curing. The temperature of the exothermic peak is superior in low-temperature curability on the low temperature side, and the DCS curve indicating the calorific value is generally sharper than broad and has higher temperature sensitivity and excellent solidification.

(2) Adhesive sheet (S) (second embodiment)
The “adhesive sheet (S)” according to the second aspect of the present invention comprises an epoxy resin (A) having two or more epoxy groups in one molecule, a thermoplastic aliphatic polyamide (B), and a mercapto group. Adhesive layer (G) composed of an adhesive composition (H) containing two or more thiol compounds (C) and an ionic liquid (D) and peelable on one or both sides of the layer It has a protective film layer (P).
The adhesive layer (G) composed of the adhesive composition (H) in the adhesive sheet (S) of the present invention exhibits moderate adhesiveness and good adhesion before curing. .
Accordingly, the adhesive sheet (S) can be pressure-bonded to the adherend with a weak pressure, and exhibits high cohesion without reacting for a long time at high temperature. It can be applied without any problems, and it is excellent in sheet suitability.

(2-1) Adhesive composition (H) and adhesive layer (G)
The epoxy resin (A), the thermoplastic aliphatic polyamide (B), the thiol compound (C), and the ionic liquid (D) contained in the adhesive composition (H) are the “ It is the same as the description content in “Adhesive composition (H)”. Further, the curing accelerator (E), the solvent (F), and the effect retarder blended in the adhesive composition (H) as necessary are the “adhesive composition” of the first aspect. (H) ”is the same as the description in“. As will be described later, the adhesive layer (G) is formed by evaporating the solvent (F) after applying the adhesive composition (H) on the protective film (P).

(2-2) Protective film (P)
The adhesive sheet (S) has at least a peelable protective film layer (P) on one or both sides of the adhesive layer (G).
A protective film layer (P) consists of a synthetic resin film and the peeling member which has the peelability laminated | stacked on this film, and has a function which protects the surface of an adhesive agent layer. The protective film layer (P) is not particularly limited as long as it has necessary strength and flexibility, and a synthetic resin film subjected to silicone release treatment is generally used. As the material of the synthetic film, for example, polyester resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polyarylate, and polytetramethylene terephthalate are preferable. In addition, although the thickness of a protective film layer (P) is not specifically limited, From points, such as maintenance of mechanical strength, 25-100 micrometers is preferable.

(2-3) Adhesive sheet (S)
The adhesive sheet (S) can be produced by the method described in "Method for producing an adhesive sheet (S)" of the third aspect of the present invention.
The thickness of the adhesive layer composed of the above adhesive composition is not particularly limited and can be appropriately selected depending on the application, but is usually 5 to 500 μm, preferably 10 to 10 μm. 50 μm. If the thickness is less than 5 μm, sufficient adhesive strength may not be obtained, and if it exceeds 500 μm, the cost is increased for performance, and sufficient adhesiveness is exhibited depending on the processing conditions. The amount of heat and pressure may be insufficient.

(2-4) Use of the adhesive sheet (S) The adhesive sheet (S) of the present invention is weak to an adherend before curing of the adhesive composition constituting the adhesive layer. It can be pressure-bonded by pressure, and can be applied regardless of the material of the adherend by curing at a low temperature and in a short time thereafter, and is excellent in durability. , And interior and exterior materials for ships, furniture such as window frames and door frames, interior materials for buildings such as walls, floors and ceilings, furniture such as desks, tables and bookshelves, and home appliances such as TVs and air conditioners. The present invention can also be applied to housings, containers, OA devices such as personal computers, and small electronic mobile housings such as mobile phones and electronic books.

(2-5) Method for Producing Adhesive Sheet (S) The production of the adhesive sheet (S) according to the third aspect of the present invention is not particularly limited, and a conventionally known method or the like is applied. For example, after the adhesive composition (H) is applied onto the peelable protective film layer (P), the solvent can be removed by evaporation.
For example, an epoxy resin (A), a thermoplastic aliphatic polyamide (B), a thiol compound (C), an ionic liquid (D) and a solvent (F), and if necessary, a curing accelerator (E), curing The adhesive composition (H) is obtained by dissolving, dispersing, and the like in the solvent (F) with the retarder and the various resins. Next, the composition (H) is coated on the entire surface of the peelable protective film layer (P) to form a precursor of the adhesive layer (G). Thereafter, the solvent (F) is evaporated and dried from the precursor to form an adhesive layer (G), and an adhesive layer (G) and a protective film layer (P) that can be peeled off on one side of the layer are provided. The adhesive sheet (S) which has can be formed.
The method for applying the adhesive composition (H) on the peelable protective film layer is not particularly limited, and a conventionally known method can be used. Examples thereof include a roll coating method, a gravure coating method, a reverse coating method, a spray coating method, an air knife coating method, a curtain coating method, a die coating method, and a comma coating method.

Furthermore, if necessary, a peelable protective film layer (P) can be laminated on the other surface of the adhesive layer (G), and the adhesive layer (G) can be peeled off on both sides of the layer. An adhesive sheet (S) having a protective film layer (P) can be formed.
Although the thickness of the adhesive agent layer (G) of this invention is not specifically limited, It is preferable that it is 5-250 micrometers, and it is more preferable that it is 10-100 micrometers. If it is the said range, since it has moderate softness | flexibility and adhesiveness (adhesion) property, handling becomes easy.

(3) Laminate (L) (Third Aspect)
The “laminate (L)” according to the third aspect of the present invention is an epoxy resin (A) having two or more epoxy groups in one molecule on a planar or three-dimensional object as an adherend. ), A thermoplastic aliphatic polyamide (B), a thiol compound (C) having two or more mercapto groups, and an adhesive composition (H) containing an ionic liquid (D) (G) ), And further heat-cured in a state where at least one resin layer (M) is laminated on the adhesive layer (G).
(3-1) Adhesive layer (G)
The adhesive layer is composed of an epoxy resin (A) having two or more epoxy groups in one molecule, a thermoplastic aliphatic polyamide (B), a thiol compound (C) having two or more mercapto groups, and an ionic property. It is a layer which consists of an adhesive composition containing a liquid (D). The adhesive layer (G) is a layer formed from the adhesive sheet (S).

(3-2) Resin layer (M)
The resin layer (M) is not particularly limited. However, in order to form a decorated laminate (L) in practice, for example, as shown in FIG. As shown in FIG. 2 (E), a layer configuration such as surface hard coat layer / primer layer / decorative printing layer can be exemplified.
A sheet (hereinafter sometimes referred to as a decorative sheet (K)) on which the decorative printing layer is printed on the easy-molding base material has good followability with respect to a three-dimensional surface, and is a decorative laminate ( L) is suitable as a decorative sheet (K) used for forming.
As the decorative print layer, usually, patterns and characters are printed on an easily molded substrate with gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, sublimation transfer printing, ink jet printing, and the like. It is formed by a printing method. The thickness of the decorative printing layer is not particularly limited, and can be appropriately selected from the viewpoint of design properties and the like.

The easily molded substrate preferably has a storage elastic modulus at 100 to 140 ° C. of 1 × 10 ⁵ to 1 × 10 ⁸ Pa. If the storage elastic modulus is within the above range, a decorative sheet having good curved surface followability can be obtained. If it is less than 1 × 10 ⁵ Pa, the appearance may be deteriorated due to film shrinkage after molding. In addition, the said storage elastic modulus shows the ease of deformation | transformation of resin etc., and can be measured by the method based on JISK7244-1 and JISK7244-4. Specifically, it can be measured using a commercially available viscoelasticity measuring device. For example, using a solid viscoelasticity analyzer RSA-II manufactured by Rheometrics Co., Ltd., a sample having a width of 5 mm in a tensile mode, a grip interval of 10 mm, a measurement frequency of 1 Hz, a measurement temperature of −50 ° C. to 150 ° C., and a temperature increase rate of 5 ° C. / Measure under the condition of minutes.

  As the easily moldable substrate, a synthetic resin film is generally used. Synthetic resin film materials include polyester resins, polypropylene resins, polyvinyl chloride resins, fluorine resins, polystyrene resins, poly (meth) acrylic resins, cellulose resins, polycarbonate resins, polyamide resins, Known resins such as polyolefin resins, polyester resins, polyvinyl alcohol resins, polyimide resins, phenol resins, polyurethane resins and the like can be mentioned. These can be used alone or in combination of two or more. Moreover, a single layer may be sufficient and the laminated body of two or more layers may be sufficient. From the viewpoint of mechanical strength, a uniaxially stretched or biaxially stretched film is preferred. In the present invention, among the above synthetic resins, polyester resins, poly (meth) acrylic resins, and urethane resins are used from the viewpoints of heat resistance, dimensional stability, rigidity, flexibility, stackability, price, and the like. Particularly preferred.

  Examples of the polyester-based resin include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polyarylate, polytetramethylene terephthalate, etc. Among them, from the viewpoint of ease of handling, low cost, etc. Polyethylene terephthalate is particularly preferred.

The thickness of the easily moldable substrate is not particularly limited, and is usually about 12 to 250 μm, preferably 25 to 250 μm. If it is the said range, mechanical strength is sufficient, it is hard to produce a curvature, a slack, a fracture | rupture, etc., workability | operativity is favorable, and it is also possible to supply and process in a continuous belt shape. If the thickness exceeds the above-mentioned thickness, excessive performance may increase the cost.
The formation method of a base material is not specifically limited, For example, conventionally well-known film forming methods, such as a solution casting method, a melt extrusion method, and a calender method, can be used. Moreover, you may use the commercially available base material previously formed into a film form by the said method.
In order to improve the wettability of the substrate, on one or both sides, a known method such as corona discharge treatment, plasma treatment, ozone treatment, flame treatment, primer treatment, preheat treatment, dust removal treatment, vapor deposition treatment, alkali treatment, etc. Easy adhesion treatment may be performed.

(3-3) Other resin layers (A) Surface hard coat layer The surface hard coat layer is the outermost layer of the laminate (L) and is a layer that suppresses deterioration from light, chemicals, and abrasion. Accordingly, those having excellent surface properties such as scratch resistance, chemical resistance and stain resistance are preferred. Specifically, acrylic resins and urethane resins are preferably used. Moreover, as other resin, a thermosetting resin composition or an ionizing radiation curable resin composition can also be used. Thermosetting resin compositions include phenolic resins, phenol-formalin resins, urea resins, urea-formalin resins, melamine resins, melamine-formalin resins, alkyd resins, epoxy resins, unsaturated polyester resins, and general-purpose two-component curing types. An acrylic resin (acrylic polyol hardened | cured material) etc. can be illustrated.
The ionizing radiation curable resin composition has an energy quantum capable of crosslinking and polymerizing molecules in electromagnetic waves or charged particle beams, that is, crosslinked and cured by irradiation with ultraviolet rays or electron beams. It refers to a resin composition. Specifically, it can be appropriately selected from polymerizable monomers, polymerizable oligomers or prepolymers conventionally used as ionizing radiation curable resin compositions.
In addition, when using an ultraviolet curable resin composition as an ionizing radiation curable resin composition, about 0.1-5 mass parts of initiators for photopolymerization may be added with respect to 100 mass parts of resin compositions. desirable.
Furthermore, the resin composition constituting the surface hard coat layer preferably contains an ultraviolet absorber. By containing the ultraviolet absorber, weather resistance can be imparted to the decorative molded product. Specific examples include salicylic acid, benzophenone, benzotriazole, cyanoacrylate, and triazine. The content of the ultraviolet absorber is preferably about 0.1 to 30% by mass in the resin composition constituting the surface hard coat layer.

Further, the resin composition constituting the surface hard coat layer may contain polyethylene wax in order to impart surface scratch resistance. The content of the polyethylene wax is preferably about 0.1 to 20% by mass in the resin composition constituting the release layer. The method for forming the surface hard coat layer is not particularly limited, and examples include a gravure coat method, a roll coat method, and a spray coat method. After coating by such a method, the solvent is evaporated by air drying or drying at a temperature of 100 ° C. or less for about 10 seconds or less. This condition is preferable because the base film does not shrink.
Moreover, it is preferable that the thickness of a surface hard-coat layer is 0.5-30 micrometers. If it is 0.5 μm or more, surface properties such as sufficient wear resistance and chemical resistance can be obtained, and if it is 30 μm or less, moldability such as shape following property can be obtained, and it is advantageous from the viewpoint of economy. is there. From the above viewpoint, the thickness of the surface hard coat layer is more preferably in the range of 1 to 10 μm.
Examples of the ionizing radiation include ultraviolet rays, electron beams, and γ rays. Examples of the energy source in the case of ultraviolet rays include ultraviolet lamps such as a low-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, an electrodeless discharge lamp, a xenon lamp, and an excimer lamp. As irradiation dose, 50-10000 mJ / cm < ² > is preferable.
In the case of an electron beam, as an electron beam source, various electron beam accelerators such as a cockroft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, a high frequency type, etc. Can be used. The acceleration voltage can be appropriately selected depending on the resin used and the thickness of the layer. Usually, the acceleration voltage is about 70 to 300 kV, and the irradiation dose is preferably such that the crosslinking density of the resin layer is saturated, and usually 5 to 300 kGy ( 0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

(B) Primer layer The primer layer is provided appropriately between the layers or on the laminate side of the base sheet in order to improve the adhesion by interposing between the layers, and a coating liquid such as urethane resin or polyester resin, It is formed by a known printing method such as gravure printing or roll coating, or a coating method. As the urethane resin and the polyester resin, resins exemplified in the adhesive layer are used. Also, instead of forming the primer layer, various known easy adhesion treatments may be performed.
(C) Decorative Print Layer The decorative print layer is a layer for imparting design properties to the decorative molded product. The printing layer is made of a suitable color pigment or a resin such as a polyvinyl resin, a polyamide resin, a polyester resin, an acrylic resin, a polyurethane resin, a polyvinyl acetal resin, a cellulose resin, or an alkyd resin. It can be formed by printing with a colored ink containing a dye as a colorant.
The printing method is not particularly limited, and examples thereof include an offset printing method, a gravure printing method, and a screen printing method.

(D) Others The pressure-sensitive adhesive layer (G) and the protective film layer may be laminated by laminating after publicly known printing, coating, or separately preparing each layer.
The molding method of the resin layer (M) is not particularly limited, and a conventionally known method can be used.
The adhesive layer (G) on one side of the adhesive sheet (S) is peeled off and attached to the resin layer (M) on the decorative sheet (K) composed of the easy-forming base material and the decorative printing layer. be able to.

(3-4) Adherent The adhesive sheet (S) of the present invention can be applied regardless of the material of the adherend. Further, the adhesive layer (G) constituting the adhesive sheet (S) of the present invention exhibits good adhesion and adhesion to an adherend and is excellent in durability. As adherends, interior materials and exterior materials for automobiles, railways and other vehicles, aircraft, and ships, furniture such as window frames and door frames, interior materials for buildings such as walls, floors, and ceilings, desks, tables, bookshelves The present invention can also be applied to furniture such as televisions, housings and containers of household electrical appliances such as TVs and air conditioners, office automation equipment such as personal computers, and small electronic mobiles such as mobile phones and electronic books. Furthermore, the adhesive sheet (S) of the present invention is pressure-bonded to the adherend with a weak pressure before the adhesive composition (H) constituting the adhesive layer (G) is cured. Since good adhesiveness and adhesion can be realized by subsequent curing at a low temperature and in a short time, it can be suitably used particularly for an integral molding method by vacuum formation.

(3-5) Manufacturing method of laminated body (L) The adhesive layer (G) of the adhesive sheet (S) used for manufacturing the laminated body (L) of the present invention is a molded article to be adhered. It can be pressure-bonded with a weak pressure against the above, and exhibits moderate tackiness and good adhesion to the decorative sheet (K) without reacting at a high temperature for a long time. Also good. As a manufacturing method of a laminated body (L), (i) water pressure transfer system, (ii) vacuum forming system, etc. which are post-molding decoration systems, (i) insert system, (ii) ) In-mold method, etc., but when using the adhesive sheet (S) of the present invention, there is an integral molding method employing a vacuum molding method in which the decorative sheet is attached to a molded product by vacuum suction. Is preferred.
For example, in the case of molding the decorated laminate (L) shown in FIG. 1C, the protective film layer 2 and the adhesive layer 1 shown in FIG. After the adhesive film 9 is used and the protective film layer 2 on one side is peeled off, the decorative print layer 3 surface of the laminate composed of the surface hard coat layer 5, the easily molded substrate 4 and the decorative print layer 3 is applied. After forming the laminated product (FIG. 1 (B)), the protective film layer 2 is further peeled off, and a vacuum forming machine is used so that the adhesive layer 1 surface and the molded body 11 surface are pressure-bonded. The inside of the apparatus is decompressed, and a laminate precursor is obtained by forming a vacuum while heating at a temperature at which the decorative sheet can be formed, for example, 100 to 140 ° C. for 10 to 120 seconds. Next, by trimming unnecessary portions, the decorated laminate (L) shown in FIG. 1C can be obtained.

  Moreover, when shape | molding the laminated body (L) by which the layer structure shown to FIG. 2 (C) is shape | molded, the protective film layer 2 and adhesive layer which can peel to both surfaces shown to FIG. 2 (A) 1 is used, and the protective film layer 2 on one side is peeled off, and then the transfer substrate 8, the release layer 7, the surface hard coat layer 5, the primer layer 6, and the decorative printing layer 3 are laminated. After adhering to the decorative print layer 3 surface of the body to form a laminate (FIG. 2B), the protective film layer 2 is further peeled, and the adhesive layer 1 surface and the surface of the molded body 11 are pressure-bonded. Thus, the inside of the apparatus is decompressed using a vacuum forming machine, and the laminated body precursor is formed by vacuum forming while heating at a temperature at which the decorative sheet can be formed, for example, at 100 to 140 ° C. for 10 to 120 seconds. Next, trimming is performed by peeling the layer composed of the transfer substrate 8 and the release layer 7 from the laminate precursor. Without, it can be obtained decorated by laminate having the layer constitution shown in FIG. 2 (C) a (L).

Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to the method described below. The raw materials and evaluation methods used in the examples and comparative examples are described below.
(1) Raw material (1-1) Epoxy resin (i) Epoxy resin 1
Solid bisphenol A epoxy resin (Mitsubishi Chemical Corporation, trade name: jER1001)
Epoxy equivalent: 450-500
(Ii) Epoxy resin 2
Dimer acid modified epoxy resin (Mitsubishi Chemical Corporation, trade name: jER872)
Epoxy equivalent: 600-700
(Iii) Poxy resin 3
NBR modified epoxy resin (trade name: EPR-4030, manufactured by ADEKA Corporation)
Epoxy equivalent: 380

(1-2) Base resin (i) Polyamide resin Aliphatic polyamide (Fuji Kasei Kogyo Co., Ltd., trade name: TAPE-826-5A, polymerized fatty acid-based polyetheresteramide block copolymer, amino group-containing)
(Ii) Polyimide resin Polyimide resin (trade name: Neoprim, manufactured by Mitsubishi Gas Chemical Co., Ltd.)

(1-3) Curing agent (i) Curing agent 1
Polymer Captan Epoxy Curing Agent (Mitsubishi Chemical Corporation, Trade Name: Epomate QX40, Mercaptan Equivalent 133)
(Ii) Curing agent 2
Triazine derivative (trade name: TSH, manufactured by Kawaguchi Chemical Co., Ltd.), wherein R _{1 in the} general formula (1) is a methyl group (—CH ₃ ), active hydrogen equivalent: 59, molecular weight: 177, powder, decomposition temperature: 300 ° C
(Iii) Curing agent 3
1,3,5-Tris (3-mercaptobutyloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione (manufactured by Showa Denko KK, trade name: Karenz MT NR1)
(Iv) Curing agent 4
Pentaerythritol tetrakis (3-mercaptobutyrate)
(Product name: Karenz MT PE1 manufactured by Showa Denko KK)
(V) Curing agent 5
Inclusion imidazole (Nippon Soda Co., Ltd., trade name: HIPA-2E4MZ, powder)

(1-4) Ionic liquid (i) Ionic liquid 1
1-butyl-3-methylpyridinium (trifluoromethanesulfonic acid) (Nippon Carlit Co., Ltd., trade name: CIL313)
(Ii) Ionic liquid 2
1-butyl-3-methylimidazolinium hexafluorophosphate (Nippon Gosei Co., Ltd., trade name: BMI-PF6)
(Iii) Ionic liquid 3
1-butyl-3-methylimidazolinium bistrifluoromethanesulfonylimide (manufactured by Nihon Gosei Co., Ltd., trade name: BMI-TFSI)

(1-5) Curing accelerator (i) Curing accelerator 1
Epoxyactuate tertiary amine (Ajinomoto Finetechno Co., Ltd., trade name: ajicure MY-H, powder)
(Ii) Curing accelerator 2
Microcapsule (aromatic amine) (Asahi Kasei E-Materials Co., Ltd., trade name: Novacure 3721)
(Iii) Curing accelerator 3
Phosphonate salt of 1,8-diazabicyclo (5.4.0) undecene-7 (manufactured by San Apro Co., Ltd., trade name: U-CAT502)

(1-6) Curing retarder n-tributyl borate (1-7) solvent Equal mass mixture of toluene and methyl ethyl ketone (MEK)

(2) Evaluation (A) Adhesive Peeling the release sheet (SP-PET-01) of the adhesive sheet obtained in Examples and Comparative Examples, and removing the base sheet (trade name: E5100, corona treatment on one side) Attached to the corona-treated surface of the resulting PET film, film thickness: 38 μm, manufactured by Toyobo Co., Ltd., then cut to 25 mm × 150 mm to prepare a test piece. This test piece was laminated on a stainless steel plate (SUS304) using a 2 kg roller. Then, using a tensile tester (manufactured by A & D, product name: RTF-1150H), the adhesive strength to the stainless steel plate surface before curing is measured (according to JIS Z0237, speed: 300 mm / min, peel distance: 150 mm, peel angle). : 180 °).
Evaluation was performed by sticking the adhesive sheets obtained in Examples and Comparative Examples to (i) SUS304 (described as “immediately after preparation” in Tables 1 to 3), and (ii) 120 ° C. after the pasting. (Iii) The adhesive sheet is stored at 40 ° C. for 120 hours and then attached to SUS304 at 120 ° C. for 2 minutes. The measurement was performed by measuring the adhesive strength after heating (in Tables 1 to 3, described as “when heated after storage”). In addition, the “material breakage (PET)” described in Tables 1 to 3 does not peel between the adhesive sheet and the base sheet (PET film), and material breakage occurs in the base sheet (PET film). Means that.

(B) Adhesive dynamic elastic modulus on a base material sheet (trade name: Soft Shine A1597, polyester film, film thickness: 50 μm, manufactured by Toyobo Co., Ltd.), acrylic resin as binder resin, silicone type Gravure printing was performed with a coating solution containing a resin as a releasable material at a coating amount of 4 g / m ² to form a release layer. On this release layer, gravure printing was performed with an acrylic printing ink using an acrylic printing ink at a coating amount of 8 g / m ² to form a decorative printing layer, whereby a decorative sheet was obtained. Then, the release sheet (SP-PET-01) of the adhesive sheet obtained in Examples and Comparative Examples is peeled off and pasted on the decorative print layer of the decorative sheet with a laminator (pressure 2 kg) at room temperature. It was. The release sheet (SP-PET-03) of the sheet is peeled off, and the inside of the apparatus is depressurized using a vacuum forming machine so that the adhesive layer surface and the adherend ABS surface are pressure-bonded. The inside of the apparatus was depressurized and vacuum formation was performed while heating at 130 ° C. for 30 seconds. After leaving it in an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH for 30 minutes, using a 2 kg roller on the surface of the outermost layer of the decorative sheet, a 50 mm long cello tape (registered trademark, model number: CT-15) , Manufactured by Nichiban Co., Ltd.), and using a tensile tester (product name: RTF-1150H, manufactured by A & D), the cellophane was peeled from the surface of the pattern layer (speed: 2000 mm / min, peel angle: 180 °). ), The surface after peeling was observed, and the adhesion was evaluated.
The evaluation criteria are as follows.
○: no peeling, Δ: peeling ratio is less than 10%, x: peeling ratio is 10% or more.

(C) Durability The adhesive sheet release sheet (SP-PET-01) obtained in the examples and comparative examples was peeled off, and a sample was prepared in the same manner as described above. It was left for 30 minutes in an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH. Then, it was left to stand in a drying oven under an atmosphere of 80 ° C. for 12 hours, and the test piece after being left was visually observed to evaluate durability. The evaluation criteria are as follows.
○: No swelling or cracks are observed, ×: swelling or cracks are observed.

(D) Shear strength The adhesive sheets obtained in the examples and comparative examples were cut into 25 mm × 10 mm, the release sheet (SP-PET-01) was peeled off, and after crimping to an alcohol-washed hot-dip galvanized steel sheet, The release sheet (SP-PET-03) is peeled off, pressure-bonded to another test piece, and heated and cured under the conditions shown in Tables 1 to 3 in a blowing oven at each temperature with a 1 kg load applied. 23 ° C.), and a measurement sample was prepared. Then, using a tensile tester (product name: RTA-1T, manufactured by A & D), the tensile shear stress at room temperature was measured (based on JIS K6850, tensile speed 0.5 mm / min).

[Examples 1 to 6]
In Examples 1-6, when an ionic liquid was mix | blended in the adhesive composition, it confirmed that adhesiveness and initial stage adhesiveness improved.
(1) Preparation and Evaluation of Thermosetting Adhesive Composition In Examples 1 to 6, the epoxy resins 1 to 3 (bisphenol type epoxy resin), the curing agent, the solvent, and the ionic liquid 1 shown in Table 1 were used. Each was sufficiently stirred using a disper (disperser manufactured by Primix Co., Ltd., model: TK homodisper 2.5 type). Thereafter, a polyamide resin, a polyimide resin (based on solid content), and a solvent were further added, and after sufficiently stirring using a disper, defoaming was performed at room temperature to prepare a thermosetting adhesive composition. The stirring condition is 15 minutes at 1000 rpm. About the obtained thermosetting type adhesive composition, storage stability, adhesiveness, and sclerosis | hardenability were evaluated.

(2) Preparation and Evaluation of Adhesive Sheet The thermosetting adhesive composition is a protective film (a polyester film having a release treatment with a silicone release agent on one side, trade name: S-PET-03 The entire surface was coated with an applicator so that the film thickness after drying was 30 μm on a release-treated surface of a film thickness of 38 μm, manufactured by Mitsui Chemicals Tosero Co., Ltd., to form an adhesive layer.
Then, it is dried for 3 minutes at 80 ° C. in a drying oven, and the release surface of the protective film (trade name: S-PET-03, film thickness 38 μm, manufactured by Mitsui Chemicals, Inc.) is laminated to the adhesive sheet. The adhesive sheets of Examples 1 to 6 were respectively prepared. About the obtained adhesive sheet | seat, the laminated body thickness measurement, adhesive force, adhesiveness, durability, and shear strength were evaluated. The evaluation results are shown in Table 1.

[Comparative Examples 1-6]
In Comparative Examples 1-6, except having added the hardening accelerator shown in Table 2 instead of the ionic liquid, the same component as having described in Examples 1-6 was added, respectively, and described in Examples 1-6 The same stirring was performed as described above to prepare a thermosetting adhesive composition. Next, using the obtained thermosetting adhesive composition, adhesive sheets were prepared in the same manner as described in Examples 1 to 6, respectively. About the obtained adhesive sheet, evaluation similar to having described in Examples 1-6 was performed. The evaluation results are shown in Table 2.
[Comparative Example 7]
In Comparative Example 7, the same components as described in Example 1 were added except that curing agents 2, 4, and 5 shown in Table 2 were added instead of curing agent 1 and a curing accelerator was not added. The same stirring as described in Example 1 was performed to prepare a thermosetting adhesive composition. Next, using the obtained thermosetting adhesive composition, adhesive sheets were prepared in the same manner as described in Example 1, respectively. The obtained adhesive sheet was evaluated in the same manner as described in Example 1. The evaluation results are shown in Table 2.

[Examples 7 to 9]
In Examples 7 to 9, the same components as described in Example 6 were added except that the ionic liquids 1 to 3 shown in Table 3 were used as the ionic liquid. The same stirring was performed to prepare a thermosetting adhesive composition. Next, using the obtained thermosetting adhesive composition, adhesive sheets were prepared in the same manner as described in Example 1, respectively. The obtained adhesive sheet was evaluated in the same manner as described in Example 1. The evaluation results are shown in Table 3.
In Example 7, since the same ionic liquid 1 as in Example 6 is used, Examples 6 and 7 are the same example, but the comparison with Examples 8 and 9 is easy. Therefore, it is described in Table 3 as Example 7.
From the evaluation results shown in Table 3, it was confirmed that in Examples 7 to 9, the same effects of adding the ionic liquid as those obtained in Examples 1 to 6 were obtained.

[Examples 10 to 13]
In Examples 10-13, the same components as described in Example 6 were added except that the ionic liquid 1 shown in Table 3 was used as the ionic liquid while changing the blending ratio thereof. The same stirring as described in 6 was performed to prepare a thermosetting adhesive composition. Next, using the obtained thermosetting adhesive composition, adhesive sheets were prepared in the same manner as described in Example 1, respectively. The obtained adhesive sheet was evaluated in the same manner as described in Example 1. The evaluation results are shown in Table 3.
In Example 11, since the same amount of the same ionic liquid 1 as in Example 6 is used, Examples 6 and 11 are the same example, but the comparison with Examples 10 to 13 is easy. Therefore, it is described as Example 11 in Table 3. From the evaluation results shown in Table 3, in Examples 10 to 13, the same effects of adding the ionic liquid as those obtained in Examples 1 to 6 could be confirmed.

1 Adhesive layer (G)
2 Protective film layer (P)
3 Decorative printing layer (K)
4 Easy Molding Base 5 Surface Hard Coat Layer 6 Primer Layer 7 Release Layer 8 Transfer Base 9 Adhesive Sheet (S)
11 Molded body 12 Molded body

Claims (5)

Epoxy resins having two or more epoxy groups in one molecule (A), a thermoplastic aliphatic polyamide (B), seen containing a thiol compound having two or more mercapto groups (C), and the ionic liquid (D) The thiol compound (C) is
(I) a polythiol having a triazine skeleton,
(Ii) a thiol compound obtained by an esterification reaction of a polyol and a mercapto organic acid,
(Iii) an alkyl polythiol compound, and
(Iv) a terminal thiol group-containing polyether,
1 or 2 types or more selected from these, The adhesive composition characterized by the above-mentioned .   The adhesive composition is formulated such that the thiol compound (C) has an active hydrogen equivalent of 0.7 to 1.2 equivalents per 1 epoxy equivalent of the epoxy resin (A), and the thiol compound ( C) 1-10 mass parts of ionic liquids (D) are mix | blended with respect to 100 mass parts, The adhesive composition of Claim 1 characterized by the above-mentioned. The polythiol having the triazine skeleton is 2,4,6-trimercapto-1,3,5-triazine,
1-hexylamino-3,5-dimercaptotriazine,
1-diethylamino-3,5-dimercaptotriazine,
1-cyclohexylamino-3,5-dimercaptotriazine,
1-dibutylamino-3,5-dimercaptotriazine,
The viscosity according to claim 1 or 2, which is one or more selected from 2-anilide-4,6-mercaptotriazine and 1-phenylamino-3,5-dimercaptotriazine. Adhesive composition. Viscosity containing an epoxy resin (A) having two or more epoxy groups in one molecule, a thermoplastic aliphatic polyamide (B), a thiol compound (C) having two or more mercapto groups, and an ionic liquid (D) the adhesive composition (H) consisting of the adhesive layer (G) and the layer of one side, or possess both sides peelable protective film layer (P), the thiol compound (C)
(I) a polythiol having a triazine skeleton,
(Ii) a thiol compound obtained by an esterification reaction of a polyol and a mercapto organic acid,
(Iii) an alkyl polythiol compound, and
(Iv) a terminal thiol group-containing polyether,
1 or 2 or more types selected from these, The adhesive sheet characterized by the above-mentioned . Two or more epoxy resins (A) having two or more epoxy groups in one molecule, thermoplastic aliphatic polyamide (B), and two or more mercapto groups on a planar or three-dimensional object as an adherend. An adhesive layer (G) composed of an adhesive composition (H) containing a thiol compound (C) and an ionic liquid (D) is laminated, and at least on the adhesive layer (G). In the state where 1 resin layer (M) is laminated, it is cured by heating, and the thiol compound (C)
(I) a polythiol having a triazine skeleton,
(Ii) a thiol compound obtained by an esterification reaction of a polyol and a mercapto organic acid,
(Iii) an alkyl polythiol compound, and
(Iv) a terminal thiol group-containing polyether,
1 type or 2 types or more selected from these, The laminated body characterized by the above-mentioned .

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