WO2009101741A1

WO2009101741A1 - Adhesive for ic card or ic tag

Info

Publication number: WO2009101741A1
Application number: PCT/JP2008/071497
Authority: WO
Inventors: Koichiro Higasa; Yoshinori Ito; Yoshinori Igarashi; Takahiro Sakurai; Yuichi Ito
Original assignee: Emulsion Technology Co., Ltd.; Toppan Forms Co., Ltd.
Priority date: 2008-02-13
Filing date: 2008-11-27
Publication date: 2009-08-20
Also published as: JP5441720B2; JPWO2009101741A1

Abstract

Disclosed is a two-liquid mixing type adhesive for an IC card or an IC tag which, in a production process, can prevent the formation of gas voids, a failure of adhesion, and a poor appearance such as warpage caused by outgas, and can prevent partial distortion that occurs in the use of an IC card or an IC tag product under high-temperature and high-humidity conditions. The adhesive for an IC card or an IC tag is a two-liquid mixing type urethane adhesive comprising a first liquid containing an isocyanate and a second liquid containing a primary hydroxyl group-containing polyol. The isocyanate (first liquid)/isocyanate group in polyol (second liquid)/hydroxyl group molar ratio is not less than 0.8 and not more than 1.1. After the mixing of the two liquids, the mixture contains not less than 0.1% by mass of an epoxy group-containing silane coupling agent. According to the above constitution, the amount of a catalyst can be reduced, and the formation of gas voids, a failure of adhesion, and warpage caused by outgas can be prevented.

Description

IC card or IC tag adhesive

The present invention relates to an IC card in which an IC module having an IC chip and an antenna is mounted inside a film, an IC card used for manufacturing an IC tag, or an adhesive for an IC tag.

2. Description of the Related Art Conventionally, there are IC cards, IC tags, and the like in which an IC module having an IC chip and an antenna is mounted inside a film, and these exchange information by short-range wireless communication using electromagnetic fields or radio waves.

The IC card has advantages in that information transmission is quick and simple, and safety against forgery and alteration is high compared to a magnetic card that has been conventionally used. Therefore, in recent years, various fields including not only financial fields such as credit cards and cash cards, but also transportation fields such as automatic ticket gates at stations and automatic toll collection on highways, and identification fields such as membership cards and registration cards. Its use is expanding in various fields.

Also, the IC tag is a minute wireless IC chip used for identifying an object, in which information such as its own identification code is recorded, and has a function of transmitting / receiving information to / from the management system using radio waves. IC tags have been developed as a product identification and management technology that replaces barcodes in the industrial world, but are not limited to this, but are attracting attention as a basic technology for promoting IT and automation in society.

As a method for manufacturing such an IC card and IC tag, a laminated sheet is obtained by laminating a skin film with an adhesive on an inlet film in which an IC module having an IC chip and an antenna is mounted on the film. There is known a method of obtaining a large number of IC cards and IC tags by separating each IC module (see, for example, Patent Document 1).

Examples of the adhesive used in this case include a hot melt film type adhesive (for example, see Patent Document 2), a hot melt type adhesive (for example, see Patent Document 3), and a one-part moisture curable adhesive (for example, Patent Document). 4), UV curable adhesives (for example, see Patent Document 5), two-component mixed adhesives (for example, see Patent Document 6), and the like have already been disclosed.

JP 2000-194814 A JP 2003-285403 A JP 2001-216492 A Japanese Unexamined Patent Publication No. 7-156582 JP 2001-184476 A JP-A-8-185498

Hot melt film type adhesives and hot melt type adhesives must be heated to at least 100 ° C. to melt the adhesive, but the IC chip built in the IC card has a thermal effect, so IC It is necessary to impart heat resistance to the chip, which increases the cost. In addition, the one-component moisture curable adhesive reacts with moisture in the atmosphere and cures, and it takes time to cure, resulting in poor production efficiency. The UV curable adhesive is cured by ultraviolet rays, and has a drawback that it does not cure unless the film to be bonded and the adhesive are transparent.

Therefore, a two-component mixed adhesive that hardens quickly at a low temperature is attracting attention as an adhesive for lamination. However, some IC cards are printed on a laminated sheet laminated with an adhesive, and then a transparent film (protective film) is superimposed on the front and back of the sheet to improve printing protection and surface smoothness. Thermal lamination may occur with a hot press. When using an isocyanate adhesive such as urethane adhesive, carbon dioxide gas is generated by the reaction of water and isocyanate in the atmosphere, and the carbon dioxide gas contained in the adhesive layer expands due to the heat of lamination, and the laminated sheet This has caused appearance defects such as bubbles in the surface and partial adhesion failure to the protective film.

In addition, the two-component mixed type adhesive is a warp of the laminated sheet due to the curing shrinkage of the adhesive, or a partial distortion caused by insufficient adhesion between the antenna metal and the adhesive under high temperature and high humidity, that is, There was still room for improvement in terms of occurrence of poor surface flatness of the product.

As described above, at present, in this application, a two-component mixed adhesive that can prevent the occurrence of bubbles, adhesion failure, warpage, and surface distortion due to the outgas of the adhesive has not been disclosed yet, The creation of such adhesives is eagerly desired by the industry.

An object of the present invention is to solve the above-described problems of the prior art, and it is not necessary to perform an adhesive treatment at a high temperature in the manufacturing process, and appearance such as bubbles due to outgas, poor adhesion, warping, etc. To provide a two-component mixed type IC card or an IC tag adhesive that can prevent defects or partial distortions that occur when an IC card or IC tag product is used under high temperature and high humidity.

As a result of intensive studies to solve the problems of the prior art as described above, the catalyst used for accelerating curing after mixing the two liquids is a reaction between the isocyanate of the first liquid and the hydroxyl group of the second liquid. At the same time, the reaction between moisture in the atmosphere and isocyanate was also promoted, and it was found that the larger the amount of catalyst added, the more bubbles and poor adhesion occur. However, if the amount of the catalyst is simply reduced, the curing is delayed and the production efficiency of the laminated sheet is reduced. Therefore, as a means for reducing the catalyst amount while maintaining the curing rate, a polyol having a high reactivity with a primary hydroxyl group is used as the second liquid polyol, and the reactivity between the isocyanate group of the first liquid and the hydroxyl group of the second liquid is used. The amount of catalyst was reduced by increasing. Further, by setting the isocyanate group / hydroxyl molar ratio to 0.8 to 1.1, excess isocyanate groups were minimized, and the opportunity for reaction with moisture in the atmosphere was reduced together with the catalyst weight reduction effect described above. Furthermore, it has been found that when a silane coupling agent having an epoxy group is contained in an amount of 0.1% or more after mixing two liquids to improve the adhesion of the adhesive to the antenna metal, partial distortion is improved. The inventors have conceived that the above-mentioned problems can be solved and completed the present invention. That is, according to the present invention, the following IC card or IC tag adhesive is provided.

[1] The first liquid contains isocyanate and the second liquid contains a polyol whose hydroxyl group is a primary hydroxyl group, and the isocyanate group / hydroxyl molar ratio of isocyanate (first liquid) / polyol (second liquid) is 0.00. At least one of the inlet films on which an IC module having an IC chip and an antenna, which is 8 or more and 1.1 or less and contains 0.1% by mass or more of a silane coupling agent having an epoxy group after mixing two liquids An IC card or IC tag adhesive, which is a two-component mixed urethane adhesive for forming a laminated sheet by laminating a skin film protecting the inlet film on the surface.

[2] The adhesive for IC card or IC tag according to [1], wherein the silane coupling agent having an epoxy group is contained in isocyanate (first liquid).

[3] The IC card or IC tag adhesive according to [1] above, wherein particles having an aspect ratio of 10 to 100 are contained in an amount of 5% by mass to 40% by mass after mixing two liquids.

According to the IC card or IC tag adhesive of the present invention, the IC card, the IC card, the IC card, the IC tag, the IC card, the IC tag, the IC Partial distortion that occurs when tags are used can be prevented.

It is sectional drawing of an IC card and an IC tag.

Explanation of symbols

1: Inlet film, 1a: base film, 2: IC chip, 3: antenna, 4: adhesive layer, 5: skin film, 6: protective film.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments, and changes, modifications, and improvements can be added without departing from the scope of the invention.

FIG. 1 shows an embodiment of a layer configuration of an IC card and an IC tag obtained by the present invention. An adhesive layer 4 is formed by a two-component mixed urethane adhesive on the mounting surface of the inlet film 1 on which the IC module having the IC chip 2 and the antenna 3 is mounted (mounted) to protect the mounting surface of the inlet film 1. A skin film 5 is laminated, and an adhesive layer 4 is formed on the surface opposite to the mounting surface of the inlet film 1 with a two-component mixed urethane adhesive, and the skin film 5 is laminated to form a laminated sheet. Has been. This is printed and the protective film 6 is further heat-laminated.

The inlet film 1 is a film on which an IC module having an IC chip 2 and an antenna 3 is mounted (mounted). Examples of the antenna 3 include a board-shaped antenna in which an antenna pattern is formed on a printed circuit board, in addition to a coil-shaped antenna in which a metal wire is wound to form a coil. The IC module includes the IC chip 2 and the antenna 3 as essential constituent members, but may further include other constituent members. Examples of such constituent members include capacitors and resistors. Generally, electrical continuity between an IC chip, an antenna, and other components is ensured by a conductive adhesive such as a silver paste, a copper paste, or a carbon paste, or a conductor such as a bonding wire. The IC chip and the antenna of the inlet film 1 function as a non-contact type IC card and IC tag by communicating with an external reader / writer.

Examples of the inlet film 1 include a structure in which an IC chip 2 and an antenna 3 are placed on the surface of a single base film 1a (see FIG. 1), and a base material having two IC chips 2 and an antenna 3. The thing of the structure (not shown) enclosed by the adhesive bond layer between the films 1a etc. is used. The maximum thickness of the inlet film 1 is about 50 to 400 μm.

Examples of the material of the base film 1a constituting the inlet film 1 include polyester resins such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene terephthalate / isophthalate copolymer; polyethylene (PE), polypropylene ( PP), polyolefin resins such as polymethylpentene; polyfluorinated ethylene resins such as polyvinyl fluoride, polyvinylidene fluoride, poly-4-fluoroethylene, ethylene / 4-fluoroethylene copolymer; 6-nylon, 6, Polyamides such as 6-nylon; polyvinyl chloride, vinyl chloride / vinyl acetate copolymer, ethylene / vinyl acetate copolymer, ethylene / vinyl alcohol copolymer, vinyl polymer such as polyvinyl alcohol, vinylon; cellulose triacetate, SE Cellulosic resins such as fans; acrylic resins such as polymethyl methacrylate, polymethacrylate ethyl, polyethyl acrylate, polybutyl acrylate; synthetic resins such as polystyrene, polycarbonate, polyarylate, polyimide; In addition to paper such as thin paper, glassine paper, and sulfate paper, single layered bodies such as metal foil, woven fabric, and non-woven fabric, or laminated sheets of two or more layers thereof can be used. Among these, PET and PP can be suitably used.

The skin film 5 is a film that covers at least one surface of the inlet film 1. The skin film 5 is bonded to the inlet film 1 via the adhesive layer 4 to form a laminated sheet, and an IC card and an IC tag are formed. The skin film 5 protects the IC chip 2 and the antenna 3. In addition, the shape of the IC card or IC tag is maintained. As the skin film 5, the same material as that constituting the base film 1a already described can be used.

As the skin film 5, a film such as white pigmented PET or PP can be suitably used by including a white pigment or air bubbles. In particular, PET whose crystallinity is controlled is a card. Since it can be embossed, it can be suitably used. Moreover, in order to improve the designability, the surface of the skin film 5 opposite to the adhesive layer 4 can be printed. Further, the printed surface of the skin film 5 is formed on the transparent protective film 6. Thermal lamination may be used to cover and protect the printed surface.

As the skin film 5, a film having a thickness of about 50 to 300 μm can be suitably used. When such a thickness is used, by setting the thickness of the adhesive layer arbitrarily, an IC card having a total thickness of 0.76 mm, which is defined by the JIS standard and is most popular, can be obtained.

In addition, the skin film 5 should just coat | cover the at least one surface of the inlet film 1, and does not necessarily need to coat | cover both the front and back surfaces of the inlet film 1. FIG. That is, in the IC tag and the IC card of the present invention, the inlet film 1 has a five-layer type in which both front and back surfaces are laminated by the adhesive layer 4 and the skin film 5, and seven layers in which both front and back surfaces are covered by the protective film 6. In addition to the type (see FIG. 1), a three-layer type in which one surface of the inlet film 1 is covered with a skin film 5 is also included.

The two-component mixed urethane adhesive forming the adhesive layer 4 for bonding the inlet film 1 and the skin film 5 includes an isocyanate in the first liquid (main agent) and a polyol that is an active hydrogen compound in the second liquid. In addition, the hydroxyl group of the polyol of the second liquid is a primary hydroxyl group. More specifically, the first liquid contains polyol, inorganic particles, synthetic zeolite, silane coupling agent and the like in addition to isocyanate such as polymeric MDI and modified MDI. The second liquid contains inorganic particles, titanium dioxide, a catalyst and the like in addition to the polyol having a primary hydroxyl group. In addition, since the polyol of 1st liquid will be made to react with isocyanate beforehand, there is no need of limitation, such as primary and secondary.

Examples of the modified MDI used in the present invention include 4,4′-diphenylmethane diisocyanate carbodiimide modified products and urethane modified products of 4,4′-diphenylmethane diisocyanate. The modified MDI may be used alone or in combination of two or more.

Examples of the polyol used in the present invention include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, trimethylolpropane, diethylene glycol, triethylene glycol, hexamethylene glycol, glycerin, 1,3-butylene glycol, and 1,4-butanediol. , Hexanetriol, pentaerythritol, sorbitol, neopentyl glycol and other polyhydric alcohols; polyether polyols obtained by addition polymerization of polyhydric alcohols and alkylene oxides such as ethylene oxide and propylene oxide; polyhydric alcohols and maleic Polyester obtained by condensation reaction with polybasic acids such as acid, succinic acid, adipic acid, sebacic acid, tartaric acid, terephthalic acid and isophthalic acid Terpolyol; polyester polyol obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone; carbonates such as diphenyl carbonate, diethyl carbonate and ethylene carbonate and hexamethylene glycol, 3-methyl-1,5 Polycarbonate polyol obtained by a transesterification method using a polyhydric alcohol such as pentanediol; a homopolymer of a polymerizable monomer containing a hydroxyl group such as hydroxyethyl acrylate, hydroxybutyl acrylate, trimethylolpropane acrylic acid monoester, or Acrylic polyol which is a copolymer with monomers copolymerizable with these (acrylic acid, methacrylic acid, styrene, acrylonitrile, α-methylstyrene, etc.); castor oil or derivatives thereof ; It can be exemplified an epoxy resin having an epoxy group at both ends, monoethanolamine, and epoxy polyol obtained by reacting a diethanolamine. The adhesive of the present invention is a two-component mixed urethane adhesive composed of an isocyanate (first liquid) and a polyol (second liquid). The polyol of the second liquid has a primary hydroxyl group in the polyol. Use things. Moreover, there is no restriction | limiting in particular in the kind of polyol in the polyol contained in 1st liquid. By using a polyol whose hydroxyl group is a primary hydroxyl group as the polyol of the second liquid, it is possible to increase the reactivity between the first liquid and the second liquid, and thus it is possible to reduce the catalyst as compared with the prior art. For this reason, the reaction between moisture in the atmosphere and unreacted isocyanate due to the catalyst can be suppressed, and the generation of bubbles and adhesion failure of the adhesive layer 4 due to outgas can be suppressed to prevent the appearance failure of the IC card and IC tag. it can.

Examples of the inorganic particles used in the present invention include mica powder, talc, kaolinite, chlorite, montmorillonite, halosite, and glass flakes. By blending the inorganic particles having a high aspect ratio, the inorganic particles are oriented in the surface direction in the adhesive layer 4, so that the shrinkage in the surface direction can be suppressed and the warpage of the laminated sheet can be suppressed. The aspect ratio of the inorganic particles is preferably 10 to 100, and is contained in an amount of 5 to 40% by mass in a two-component mixed urethane adhesive composed of an isocyanate (first liquid) and a polyol (second liquid). preferable. When, for example, calcium carbonate having an average aspect ratio of 5 or less is used as the inorganic particles, the warp height is 1 mm or more, which is not preferable.

Examples of the synthetic zeolite used in the present invention include A type powder synthetic zeolite and X type powder synthetic zeolite. Synthetic zeolite functions as a moisture adsorbent. When the synthetic zeolite is not added, when mixed with the second liquid, the water in the second liquid reacts with the isocyanate of the first liquid to generate carbon dioxide gas, which may cause foaming or outgassing.

Examples of the titanium dioxide used in the present invention include rutile type titanium dioxide and anatase type titanium oxide. By inserting titanium dioxide, the IC card can be made light-impermeable.

As the silane coupling agent used in the present invention, those having an epoxy group are preferable. Specifically, in addition to γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycid Mention may be made of xylpropyltriethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These silane coupling agents may be used alone or in combination of two or more. Of these silane coupling agents, γ-glycidoxypropyltrimethoxysilane is preferably used. By blending an adhesive with a silane coupling agent having an epoxy group, the adhesion of the inlet film 1 to the metal member (antenna 3 or the like) is improved. As a result, even when the card is at high temperature and high humidity, only the portion of the laminated sheet where the metal member is present swells, water enters the interface between the metal member and the adhesive, and the metal member rusts, resulting in a circuit failure. The phenomenon that the rust portion swells can be suppressed. Moreover, the silane coupling agent having an epoxy group needs to be contained in an amount of 0.1% by mass or more after mixing the two liquids in order to prevent the occurrence of surface swelling and distortion. If an excessive amount of an epoxy group-containing silane coupling agent is added, the viscosity is lowered, and undesirable effects such as separation and sedimentation occur.

Examples of the catalyst used in the present invention include tertiary amines such as aliphatic amines (trimethylamine, triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-octylamine, diethyl-1-propylamine). Alicyclic amines (N-methylpyrrolidine, N-ethylpyrrolidine, N-methylhexamethyleneimine, N-ethylhexamethyleneimine, N-methylformolin, N-butylformolin, N, N'-) Dimethylpiperazine, N, N′-diethylpiperazine, 1,5-diazabicyclo (4,3,0) -5-nonene, 1,8-diazabicyclo (5,4,0) undecene-7 and salts thereof, 6- ( 2-hydroxypropyl) -1,8-diazabicyclo (5,4,0) undecene-7, pyridine, 4-dimethyl Minopyridine, picolines, 1-methylimidazole, 1,2-dimethylimidazole, 1,4-dimethyl-2-ethylimidazole, 1,2-dimethylimidazoline, 1,2,4-trimethylimidazoline, 1,4-dimethyl- 2-ethylimidazoline, etc.). Examples of the organic tin compound include dibutyltin dilaurate, dioctyltin dimaleate, dibutyltin phthalate, stannous octylate, dibutyltin methoxide, dibutyltin acetylacetate, and dibutyltin diversate. These catalysts may be used alone or in combination of two or more. The present invention uses a polyol that is a highly reactive primary hydroxyl group for the polyol of the second liquid, and increases the reactivity of the isocyanate group of the first liquid and the hydroxyl group of the second liquid, while maintaining the curing rate. Reduce the amount of catalyst than before. Examples of the catalyst that can obtain a high curing rate with a small addition amount include 1,8-diazabicyclo (5,4,0) undecene-7 and dibutyltin dilaurate. In the present invention, the amount of catalyst can be reduced to ½ or less compared to the prior art, and these catalysts suppress the reaction between moisture and isocyanate in the atmosphere by combining with a polyol that is a primary hydroxyl group. Thus, it is possible to effectively prevent poor adhesion and generation of bubbles due to outgassing.

The manufacturing method of the IC card and IC tag of the present invention will be described. After the above-mentioned adhesive is applied to at least one surface of the inlet film 1 and the skin film 5, the inlet film 1 and the skin film 5 are bonded together. Then, a method of sandwiching a laminated sheet for a certain period of time with a heating press plate, a method of sandwiching a laminated sheet with a pair of parallel caterpillar heating press plates for a certain period of time (see Japanese Patent Laid-Open No. 2003-162697), and a pair of parallel heating conveyor belts Heat and cure by a method of sandwiching for a certain time. In the two-component mixed urethane adhesive of the present invention, this curing step can be performed at a temperature of 20 to 150 ° C. However, if the curing step is performed at a temperature lower than 50 ° C., the curing step takes time. Since productivity falls, it is not preferable. On the other hand, when the curing step is performed at a temperature exceeding 100 ° C., it is necessary to use an IC chip having high heat resistance like the hot melt adhesive, which is not preferable because it leads to an increase in cost.

As described above, in the two-component mixed urethane adhesive of the present invention, by using a polyol having a primary hydroxyl group in the second liquid, the reactivity between the first liquid and the second liquid is increased. Since the amount of catalyst used is smaller than before, outgas is less generated from the adhesive, and even when the protective film is heat-laminated, generation of bubbles and poor adhesion of the protective film are unlikely to occur. Further, when the protective film is not laminated, it is not necessary to heat at a high temperature, so that the cost of the constituent members can be reduced.

Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

In Examples and Comparative Examples, polymeric MDI, modified MDI, polyol, inorganic particles, synthetic zeolite, titanium dioxide, silane coupling agent, and catalysts described below were used.

(1) Polymeric MDI: 4,4′-diphenylmethane diisocyanate polymer (trade name: Sumidur 44V-20, NCO content 31% by mass, average functional group number 2.5, manufactured by Sumika Bayer Urethane Co., Ltd.)

(2) Modified MDI: 4,4′-diphenylmethane diisocyanate carbodiimide modified product (trade name ISONATE 143LJ, NCO content 29 mass%, average functional group number 2, manufactured by Dow Chemical Japan).

(3) Polyol (A): Polypropylene glycol polyol having an average molecular weight of 1,000 (trade name: Actol P22, average number of functional groups 2, hydroxyl group secondary, manufactured by Mitsui Chemicals Polyurethanes).

(4) Polyol (B): Polytetramethylene ether glycol polyol having an average molecular weight of 650 (trade name: PTMG650, average number of functional groups 2, hydroxyl group 1 grade, manufactured by Mitsubishi Chemical Corporation).

(5) Polyol (C): Polycarbonate polyol having an average molecular weight of 500 (trade name: Plaxel CD 205PL, average number of functional groups 2, hydroxyl primary, manufactured by Daicel Chemical Industries).

(6) Polyol (D): Polyester polyol having an average molecular weight of 500 (trade name: Kuraray polyol P510, average number of functional groups 2, hydroxyl group 1 grade, manufactured by Kuraray Co., Ltd.).

(7) Polyol (E): Polypropylene glycol polyol having an average molecular weight of 700 (trade name: ADEKA polyether P700, average functional group number 2, hydroxyl group secondary, manufactured by ADEKA Corporation).

(8) Polyol (F): Castor oil-based polyol having an average molecular weight of 1000 (trade name: URIC H35, average functional group number 3, hydroxyl group secondary, manufactured by Ito Oil Co., Ltd.).

(9) Inorganic particles (A): Mica powder having an average particle diameter of 23 μm and an average aspect ratio of 70 (trade name: A-21S, manufactured by Yamaguchi Mica Industry Co., Ltd.).

(10) Inorganic particles (B): Mica powder having an average particle size of 5.1 μm and an average aspect ratio of 30 (trade name: SJ-005, manufactured by Yamaguchi Mica Industry Co., Ltd.).

(11) Inorganic particles (C): calcium carbonate having an average particle diameter of 1.5 μm and an average aspect ratio of 5 or less (trade name: NS600, manufactured by Nitto Flour Industries).

(12) Synthetic zeolite: 5A type powder synthetic zeolite having an average particle diameter of 2 to 4 μ (trade name: ZEOSTAR CA110P, manufactured by Nippon Chemical Industry Co., Ltd.).

(13) Titanium dioxide: Rutile-type titanium dioxide having an average particle size of 0.21 μm (trade name: Taipei CR63, manufactured by Ishihara Sangyo).

(14) Silane coupling agent: γ-glycidoxypropyltrimethoxysilane (trade name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.).

(15) Catalyst (A): 1,8-diazabicyclo (5,4,0) undecene-7 (manufactured by Sun Apro).

(16) Catalyst (B): Dibutyltin dilaurate (trade name: ADK STAB BT11, manufactured by Adeka).

Measured and evaluated as follows. In Examples and Comparative Examples, the evaluation was performed by performing the following tests.

(1) Curing speed: Curast meter (manufactured by A & D), die shape: ISO6502 flat plate die rotorless cure meter, amplitude angle: 1/4 degree, adhesive at 70 ° C. The time until the torque reached 1.0 kg · cm was measured by curing. As a result, the case where the torque reached 1.0 kg · cm in less than 5 minutes was marked as “◯”, and the case where the torque reached 1.0 kg · cm in 5 minutes or more was marked as “X”.

(2) For the evaluation of outgas, warpage, and strain, the following test pieces were prepared and used as specimens. An adhesive film is applied to PET (trade name: PET-G film (thickness: 100 μm)) with controlled crystallinity, and an antenna coil is formed of aluminum foil on one side of the inlet film (PET film (thickness: 50 μm)) ) With the antenna side facing the adhesive side, and the adhesive is cured by pressing with a 70 ° C. hot press with 500 μm spacers arranged at the four corners of the hot plate, and the PET-G / adhesive / inlet A three-layer laminated sheet having a total thickness of 500 μm was formed. The thickness of the adhesive layer of this three-layer laminated sheet was 350 μm at the maximum thickness portion. The same adhesive is applied again to the inlet film surface of this three-layer laminate sheet, and PET (trade name: PET-G film (thickness: 100 μm)) with controlled crystallinity is overlaid, and a 750 μm spacer is placed on the hot plate. The adhesive is cured while pressing with a 70 ° C hot press placed at the four corners to form a 5-layer laminated sheet with a total thickness of PET-G film / adhesive / inlet film / adhesive / PET-G film of 750 μm. did. The thickness of the adhesive layer formed in the second time of the five-layer laminated sheet was 150 μm at the maximum thickness portion. This 5-layer laminated sheet was punched into a rounded shape with a width of 54 mm, a length of 85.6 mm, and a radius of 3.18 mm at the four corners, and a card-like test piece was left at 23 ° C. and 50% RH for 3 days or longer. And then used. In the outgas evaluation, the card-like test piece was left in an atmosphere of 150 ° C. for 15 minutes, and the evaluation was made based on whether or not the warped bulge caused by the outgas occurred on the surface of the card-like test piece. The number of swelling is less than 10 per cm ² , the number of swelling is 10 or more and less than 50 / cm ² is ○, and the number of swelling is 50 or more / cm ² is ×. .

(3) Warpage evaluation (warp height) is the maximum displacement (card thickness) caused by warpage of a card-like test piece placed in a convex direction on a horizontal plane in accordance with JIS X 6305-1 5.1 “Card warp”. The maximum height including 1) was read.

(4) Evaluation of distortion (surface distortion) is as follows: a card-like test piece is left for 14 days in an environment of 60 ° C. × 90% RH; What occurred was marked as x.

(5) In the overall evaluation, in the 70 ° C. curing rate, outgas, warp height, and surface strain evaluation, all evaluations of “◯” or more were evaluated as “comprehensive evaluation ○”, and those having one or more × were determined as “total evaluation ×”.

Table 1 shows the first liquid and Table 2 shows the second liquid.

Preparation Example 1 prepared a first liquid (main agent) of a two-liquid mixed adhesive having the composition shown in Table 1. Specifically, 30 parts by mass of polyol (A) is added to 32 parts by mass of the modified MDI, and the mixture is reacted at a temperature of 90 ° C. for 2 hours to be prepolymerized. Then, 18 parts by mass of polymeric MDI and 0 ° C. moisture at 110 ° C. Add 17.5 parts by mass of inorganic particles (A) dried to less than 1%, 2.5 parts by mass of synthetic zeolite, and further add 1.3 parts by mass of a silane coupling agent to 100 parts by mass of these mixtures. Were mixed to prepare a composition (Liquid A) having the composition shown in Table 1. The NCO content of Liquid A was 12.2% by mass.

Preparation Examples 2 to 9 were the same as Preparation Example 1, and prepared a first liquid of a two-component mixed adhesive having the composition shown in Table 1.

Preparation Example 10 prepared a second liquid of a two-liquid mixed adhesive having the composition shown in Table 2. Specifically, 35 parts by mass of inorganic particles (A) dried at 110 ° C. to a moisture content of less than 0.1% and 5 parts by mass of titanium dioxide are added to 60 parts by mass of polyol (A). A composition (liquid J) having the composition shown in Table 2 was prepared by adding and mixing 0.083 parts by mass of the catalyst (A) with respect to parts by mass.

Preparation Examples 11 to 23 were prepared in the same manner as Preparation Example 10 to prepare a second liquid of a two-liquid mixed adhesive having the composition shown in Table 2.

Tables 3 and 4 show the mixing ratio of the first liquid and the second liquid and the test results. Table 3 shows examples and Table 4 shows comparative examples. The 1st liquid and the 2nd liquid were mixed with the mass mixing ratio of Table 3 and Table 4, and 70 ° C hardening time was measured. Moreover, the card-like lamination sheet was created and the outgas, the curvature height, and the surface distortion were evaluated.

(Examples 1 to 3, Comparative Examples 1 to 4)
In Examples 1 to 3, where the hydroxyl group of the polyol of the second liquid is primary, there was little swelling due to outgas, and the curing rate was sufficient. Therefore, in Examples 1 to 3, it was confirmed that the production efficiency of the laminated sheet was high because of the sufficient curing rate, and that bubbles and poor adhesion due to outgassing were less likely to occur. On the other hand, in Comparative Examples 1 to 4 in which the hydroxyl group of the polyol of the second liquid is secondary, sufficient curing rates were not obtained in Comparative Examples 1 and 3 with a small amount of catalyst, and the curing rate was increased by increasing the amount of catalyst. In Comparative Examples 2 and 4, it was predicted that outgassing increased and bubbles and poor adhesion were likely to occur.

(Examples 1, 4 and 5, Comparative Examples 5 and 6)
In Examples 1, 4, and 5 in which the molar ratio of isocyanate group / hydroxyl group in the first liquid / second liquid was 0.8 or more and 1.1 or less, there was little swelling due to outgas, and the curing rate was sufficient. Therefore, in Examples 1, 4 and 5, it was confirmed that the production efficiency of the laminated sheet was high because of the sufficient curing speed, and that bubbles and poor adhesion due to outgassing were less likely to occur. On the other hand, in Comparative Example 5 where the molar ratio of isocyanate group / hydroxyl group was 0.7, a sufficient curing rate was not obtained, and it was confirmed that the production efficiency of the laminated sheet was inferior. Further, in Comparative Example 6 in which the molar ratio of isocyanate group / hydroxyl group was 1.2, it was expected that outgassing was increased and bubbles and poor adhesion were likely to occur.

In Examples 1 and 6 containing tertiary amines or organic tin as a catalyst, it is confirmed that the production efficiency of the laminated sheet is high because bubbles are sufficiently cured, and that bubbles and adhesion failure due to outgassing are less likely to occur. done.

(Examples 1 and 7, Comparative Examples 7 to 9)
It was confirmed that Examples 1 and 7 in which the inorganic particles contained particles having an aspect ratio of 10 or more and 100 or less after mixing two liquids contained 5% by mass or more and 40% by mass or less had a small warp height. On the other hand, in Comparative Example 7 in which the aspect ratio of the inorganic particles was less than 10, the warp height was larger than in Examples 1 and 7. Further, in Comparative Example 8 in which the content of inorganic particles having an aspect ratio of 10 or more and 100 or less is less than 5% by mass, the warp height was larger than those in Examples 1 and 7. Comparative Example 9 in which the content of the inorganic particles having an aspect ratio of 10 or more and 100 or less is 40% by mass or more has a warp height equivalent to that of Examples 1 and 7, but the amount of outgas increases and bubbles and poor adhesion occur. The outbreak was expected to occur easily.

(Examples 1, 8 to 10, Comparative Example 10)
In Examples 1, 8 to 10 containing 0.1% or more of the silane coupling agent after mixing two liquids, there is almost no surface distortion even after being left for 14 days in an environment of 60 ° C. × 90% RH. I was able to confirm. On the other hand, Comparative Example 10 to which no silane coupling agent was added had a larger surface distortion in the portion containing the aluminum antenna than Examples 1 and 8 to 10, and adhered to the aluminum antenna by wet heat while using the card product. It was expected that the agent layer was easily peeled off.

(Examples 1 and 11 and Comparative Example 11)
Example 1 in which the hydroxyl groups of the polyol of the second liquid are all primary and Example 11 in which the primary / secondary molar ratio of the hydroxyl groups of the polyol of the second liquid is 90/10 are less swollen by outgas. The curing speed was sufficient. Therefore, it was confirmed that the production efficiency of the laminated sheet was high, and that bubbles and poor adhesion due to outgassing were less likely to occur. On the other hand, in Comparative Example 11 in which the primary / secondary molar ratio of the hydroxyl group of the polyol of the second liquid was 50/50, it was predicted that outgassing increased and bubbles and poor adhesion were likely to occur.

The IC card and IC tag adhesive of the present invention is not only used in the financial field such as credit cards and cash cards, but also in the field of transportation such as automatic ticket gates at stations and automatic toll collection on highways, membership cards, registration cards, etc. It can be applied to IC cards in various fields including the field of identification. It can also be applied to an IC tag used for identifying an object.

Claims

The first liquid contains isocyanate and the second liquid contains a polyol whose hydroxyl group is a primary hydroxyl group, and the isocyanate group / hydroxyl molar ratio of isocyanate (first liquid) / polyol (second liquid) is 0.8 or more and 1 .1 or less and containing 0.1 mass% or more of a silane coupling agent having an epoxy group after mixing two liquids on at least one surface of an inlet film on which an IC module having an IC chip and an antenna is mounted An IC card or IC tag adhesive which is a two-component mixed urethane adhesive for forming a laminated sheet by laminating a skin film protecting the inlet film.
The IC card or IC tag adhesive according to claim 1, wherein the silane coupling agent having an epoxy group is contained in an isocyanate (first liquid).
The IC card or IC tag adhesive according to claim 1, wherein particles having an aspect ratio of 10 or more and 100 or less are contained in an amount of 5% by mass or more and 40% by mass or less after mixing the two liquids.