JP2014065781A - Production method of laminate member and hot melt resin composition used for the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hot melt resin composition that can suppress damage to an adherend even when adhering an adherend that is weak to heat, and that is excellent in a heat degradation property over a long period, moist heat resistance, long period reliability, adhesion characteristics, and productivity or the like; and a production method of a laminate member using the same.SOLUTION: Provided is a production method of a laminate member that is formed by that two or more adherends that include at least one adherend in which heat allowable temperature is at most 80°C are mutually laminated. In the production method of a laminate member, a hot melt resin composition in which Tanδ at 80°C measured by a rheometer is 0.2-1.0 is applied to an adherend, next it is superposed with an adherend to be adhered.

Description

  In the present invention, at least one of the adherends is an adherend that is weak against heat, and when bonding using a hot melt resin composition, bonding is possible at a temperature and pressure much lower than conventional. The present invention relates to a method for manufacturing a laminated member that provides a method and enables bonding of a heat-sensitive recording material, printed matter, photograph, etc. that is weak to heat, or a package that encloses a content that cannot maintain its original quality by applying heat. .

  Conventionally, when heat-sensitive recording materials, printed materials, photographs, and other adherends that are weak to heat, or packages that contain contents that cannot be maintained by applying heat in addition to such heat-sensitive materials, etc. Are bonded using a double-sided tape that can be bonded at room temperature without applying heat, or a reactive liquid resin adhesive that is liquid at room temperature.

  Double-sided tape is characterized by its strong adhesive force immediately after being bonded at room temperature. However, the double-sided pressure-sensitive adhesive tape uses a pressure-sensitive adhesive composition such as an acrylic resin previously formed on a support such as a non-woven fabric in the form of a sheet. There is also a problem that the manufacturing cost is higher than in the case where the coating is applied in-line. In addition, it is difficult to reuse the release paper used for the adhesive surface, which is a problem because it becomes industrial waste as it is.

  On the other hand, as a reactive liquid resin, for example, a two-component epoxy resin or a urethane resin has been generally used. In this method, the main agent and the curing agent are mixed in a certain ratio, adhered at a low viscosity, and allowed to react by curing and completely solidified. However, this method has a problem that it is necessary to precisely adjust the mixing ratio of the two liquids and that the usable period is short after mixing. Moreover, since the curing period for hardening is required, there also exists a problem that productivity is low.

  In view of such problems, a hot-melt resin is an example of an adhesive resin that replaces the two-component reactive resin. The hot melt resin can reduce the viscosity at the time of application only by heating and melting, and is cooled and solidified to exhibit performance, so that the productivity is greatly improved. In addition, since a thermoplastic resin is generally used, it is possible to easily recycle the member by heating and melting and removing the resin even after the end of the product life.

  For bonding, there are polyamide-based and polyester-based hot melt resins that exhibit high adhesion to various materials. Polyamide-based hot-melt resins have low viscosity and are excellent for applying spirally from thin nozzles such as spiral spray and summit spray, and also have low shrinkage and excellent adhesiveness. Adhesiveness can be improved (for example, refer patent documents 1 to 3).

  However, the polyamide-based hot melt resin has a short solidification time, and when applied to an adherend by spraying or the like, it is necessary to bond in a very short time of several seconds. There is a problem that does not fit. Moreover, since it has high hygroscopicity, moisture absorbed from the outside by gradually absorbing moisture from the outside vaporizes all at once and becomes bubbles, so that continuous sprayability may not be obtained. In addition, the thermal stability is poor, and skin heating and carbides are generated on the molten surface during heating, so that there is a problem that the quality of the bonded structure is liable to deteriorate and the color tone is greatly changed. On the other hand, since polyester is easily hydrolyzed, there is a problem in long-term durability under high temperature and high humidity, and the adhesive strength is reduced.

  The hot melt resin composition is usually applied by a known method such as roll coating, curtain coating, bead coating, atomizing spray, spiral spray, etc. Among them, in the methods such as roll coating and curtain coating, 160 to There was a problem that the hot melt heated to 200 ° C. caused thermal damage to the adherend that is sensitive to heat, thereby deteriorating the quality of the bonded structure itself.

  As described above, the atomizing spray is cooled by the air until the hot melt resin discharged at a high temperature as described above is applied to the adherend. However, since the discharged hot melt resin is discontinuous fine particles, all of the discharged hot melt resin does not apply to the adherend, and part of it rises and is disadvantageous in terms of cost. There was also a problem that a part of the adherend and equipment that do not need to be contaminated were contaminated.

  As a method for solving these problems, there is bead coating in which hot melt is discharged linearly. However, when the bead coating is peeled off in the flow direction of the line, a stable peeling strength can be obtained, but when peeled off in the direction perpendicular to the coating direction, the bonded portion and the non-bonded portion are intermittently separated. Since it is repeated, it is not preferable.

  In addition, when bonding adherends to each other, it is necessary to bond them with a relatively high pressure. Therefore, when adhering soft adherends to each other, the adherends may be damaged.

  The hot melt resin composition application method is changing from the conventional bead method to a method in which the resin composition is applied in the form of a thread from a thin nozzle, and has excellent adhesive properties with little change in quality due to long-term melt retention. There is a need for a hot melt resin composition.

  Therefore, there is a demand for a hot-melt resin composition that has few changes in color tone and generation of carbides even when continuously heated and has various properties such as adhesive properties, hydrolysis resistance, and productivity. .

Japanese Patent Laid-Open No. 10-7993 JP 2000-202348 A JP-A-3-146160

  The present invention has been made to solve the above problems, and even when an adherend that is weak against heat is bonded, damage to the adherend can be suppressed, and long-term thermal deterioration, moist heat resistance, long-term An object of the present invention is to provide a hot melt resin composition excellent in reliability, adhesive properties, productivity, and the like, and a method for producing a laminated member using the same.

  As a result of intensive studies to solve the above problems, a hot melt resin composition having a Tan δ measured by a rheometer at 80 ° C. of 0.2 to 1.0 was applied to the adherend, and then the adherend and By superimposing and adhering, it suppresses the generation of carbides during heating, is excellent in hydrolysis resistance, and can be bonded in a state where the adherend surface is kept smooth with very little damage even on an adherend that is weak against heat. As a result, the present invention has been completed.

That is, the present invention relates to the following.
(1) A method for producing a laminated member formed by laminating a plurality of adherends including at least one adherend having an allowable heating temperature of 80 ° C. or less, wherein Tan δ measured by a rheometer at 80 ° C. The manufacturing method of the laminated member which apply | coats the hot-melt resin composition which is 0.2-1.0 to a to-be-adhered body, and then superimposes and adhere | attaches to a to-be-adhered body.
(2) The hot-melt resin composition comprises a hydrogenated styrene block copolymer (A), a polybutene (B) having a kinematic viscosity at 10O <0> C of 10 to 2,000 mm < ² > / s, and a softening point by the ring and ball method of 85 to 85. The manufacturing method of the laminated member as described in (1) containing the tackifying resin (C) which is 125 degreeC.
(3) The tackifier resin (C) is a hydrogenated tackifier resin and is at least one of a dicyclopentadiene polymer and a copolymer of dicyclopentadiene and a styrene derivative (including styrene). A method for producing a laminated member according to (2).
(4) The method for producing a laminated member according to (2) or (3), wherein the content of the oil component is 5% by mass or less in the hot melt resin composition.
(5) The method for producing a laminated member according to any one of (1) to (4), wherein a tangential vector with respect to the application locus of the hot melt resin composition applied to the adherend exhibits a directionality of 360 degrees.
(6) The method for producing a laminated member according to any one of (1) to (5), wherein the application locus of the hot melt resin composition applied to the adherend is spiral.
(7) A hot melt resin composition used in the method for producing a laminated member according to any one of (1) to (6), wherein the hydrogenated styrene block copolymer (A) has a kinematic viscosity at 100 ° C. of 10 A hot melt resin composition containing a polybutene (B) of ˜2,000 mm ² / s and a tackifying resin (C) having a softening point of 85 to 125 ° C. by the ring and ball method.

  Suppresses the generation of carbides during heating and uses extremely low heat damage to the adherend, providing excellent long-term thermal degradation, moist heat resistance, long-term reliability, adhesive properties, productivity, etc. It has become possible to provide a hot-melt resin composition and a method for producing a laminated member using the same.

It is a top view which shows the state by which the hot-melt resin composition was continuously apply | coated to the to-be-adhered body surface spirally. It is a schematic diagram which shows the measuring method of the shear strength of a laminated member.

  Hereinafter, embodiments of the present invention will be described in detail.

  The present invention relates to a method for producing a laminated member formed by bonding a plurality of adherends including at least one adherend having an allowable heating temperature of 80 ° C. or lower, and measured with a rheometer at 80 ° C. Is a method for producing a laminated member in which a hot-melt resin composition having a thickness of 0.2 to 1.0 is applied to an adherend, and then bonded to the adherend in an overlapping manner.

  An adherend having an allowable heating temperature of 80 ° C. or less is a material that cannot maintain its original quality by applying heat exceeding 80 ° C., for example, a heat-sensitive recording material, printed matter, photograph, shoji paper, paper , Batteries, films, sheets and the like, but are not limited thereto.

Tan δ measured by a rheometer at 80 ° C. of the hot melt resin composition used in the method for producing a laminated member of the present invention is 0.2 to 1.0, preferably 0.3 to 0.8. When Tan δ is in the range of 0.2 to 1.0, the hot melt resin composition is applied to the adherend accurately and in a regular locus without being dispersed.
Tan δ is the ratio of the loss elastic modulus G ″ to the storage elastic modulus G ′, and the measurement conditions are generally a measurement temperature of 80 ° C. and a frequency of 1 to 10 Hz.

  Tan δ is measured using a rheometer, and Tan δ (1 Hz) and Tan δ (10 Hz) mean Tan δ at frequencies of 1 Hz and 10 Hz, respectively. A rheometer (dynamic viscoelasticity measuring device) is, for example, a coaxial rotating cylindrical rheometer, which is used when a liquid sample is injected between an inner cylinder and an outer cylinder and the cylinder or outer cylinder is rotated. This is a device for detecting the resistance force (shear stress) of the generated liquid with a torque sensor, and examples thereof include a rheometer AR2000ex manufactured by TA Instruments.

The method for applying the hot melt resin composition to the adherend is not particularly limited, and examples thereof include known methods such as air spray, spiral spray, summit spray, roll coat, curtain coat, bead coating, and atomizing spray. However, spiral spray and summit spray are preferable in that they are applied to the adherend surface with a regular trajectory.
In particular, since the summit spray can be applied without touching the adherend, it can be applied even if the adherend is smooth or non-smooth and the heating part does not directly contact the adherend. Damage can be reduced. The discharge direction can be adjusted vertically and horizontally, and the application amount can be easily adjusted. Furthermore, a small amount of hot melt resin composition can be sprayed over a large area, and the length, fiber diameter, fiber thickness, and pattern of the coated hot melt resin composition can be changed by changing the discharge amount, gas amount, and blowing method. Can be changed. In addition, when using a hot melt resin composition having a Tan δ measured by a rheometer at 80 ° C. of 0.2 to 1.0, it is particularly easy to spray a small amount of the hot melt resin composition over a large area. Therefore, the amount of application to the adherend is reduced, and further, heat damage to the adherend can be reduced.

  The application trajectory of the hot melt resin composition applied to the adherend is preferably a continuous or discontinuous, regular trajectory, but the tangent vector with respect to the application trajectory shows a directionality of 360 degrees. preferable. That the tangent vector with respect to the application locus indicates a directionality of 360 degrees means that it has a portion facing all directions of 360 degrees. For example, as shown in FIG. A state in which the composition 2 is continuously applied in a spiral manner to the surface of the adherend 1 is exemplified. In addition to the spiral shape shown in FIG. 1, a coil shape, a loop shape, a circular shape, an elliptical shape, or the like having one turn or more can be given.

  If Tan δ of the hot melt resin composition is out of the above range (0.2 to 1.0), there is a possibility that a regular spiral coating locus may not be formed, and there is a possibility that the coating amount may be uneven. Further, the coating amount is partially increased, which is not preferable from the viewpoint of cost and heat damage to the adherend.

It goes without saying that the pattern shape such as the application trajectory changes depending on the characteristics of the hot melt resin composition and application conditions. For example, a summit spray nozzle (nozzle diameter: 0.45 mm) manufactured by Nordson is used as the summit spray. A hot melt resin composition having a Tan δ of 0.2 to 1.0 as measured with a rheometer at 80 ° C. is applied to an application amount of 50 to 80 g / m ² , and an applicator temperature (gun part 170 ° C., hose part 140 to 160 ° C., melter part 140 to 160 ° C.), coating distance 20 mm, and coating speed of 12 m / min on the adherend, a fibrous hot melt resin composition having a thickness of 90 to 130 μm on the adherend However, it is applied in a state of being meandered in the application direction at substantially equal intervals or continuously spirally.

In the method for producing a laminated member of the present invention, the adherends are preferably overlapped and bonded together in a non-heated state. For example, in a room temperature (10 to 35 ° C.) state, a pressure of 0.01 to 1 MPa is applied to the laminated adherend for about 3 to 10 seconds to produce a laminated member. In addition, you may heat in the range which the temperature of a to-be-adhered body does not exceed 80 degreeC before adhere | attaching.
By heating in a room temperature (10 to 35 ° C.) state or in a range not exceeding 80 ° C., it becomes possible to reduce thermal damage to the adherend having an allowable heating temperature of 80 ° C. or less. From the viewpoint of the adhesive properties of

The hot melt resin composition used in the method for producing a laminated member of the present invention may have a Tan δ measured by a rheometer at 80 ° C. of 0.2 to 1.0, preferably a hydrogenated styrene block copolymer. It contains a coalescence (A), a polybutene (B) having a kinematic viscosity at 100 ° C. of 10 to 2,000 mm ² / s, and a tackifying resin (C) having a softening point by the ring and ball method of 85 to 125 ° C. . Furthermore, the hot melt resin composition preferably has an oil component content of 5% by mass or less. Furthermore, it is particularly preferable not to include an oil component, and it is better not to add an oil component intentionally. When the content of the oil component is 5% by mass or less, the effect of improving the heat resistant creep property is obtained.

  Examples of the hydrogenated styrene block copolymer (A) contained in the hot melt resin composition used include, for example, isoprene of a styrene-isoprene-styrene block copolymer in which the space between the styrene polymer blocks at both ends is an isoprene polymer block. It can be obtained by hydrogenating the polymer part.

(A) As a hydrogenated styrene block copolymer, it is preferable that 200 degreeC MFR (melt flow rate, 200 degreeC, 10 kg load) is 5-100 g / 10min. When 200 degreeC MFR exceeds 100 g / 10min, the heat resistance of a hot-melt resin composition falls, and when less than 5 g / 10min, there exists a possibility that spray property may fall by the increase in a viscosity.
The 200 ° C. MFR is usually measured according to JIS K7210.

  The content of styrene in the hydrogenated styrene block copolymer (A) used is preferably in the range of 5 to 40 mass%, more preferably 10 to 30 mass%. If the content is less than 5% by mass, the viscosity of the hot melt adhesive is increased and there is a problem that the heat resistance is lowered. If the content exceeds 40% by mass, the hardness becomes too hard, which is not preferable. .

  As a commercially available product of hydrogenated styrene block copolymer (A), Kraton G1657 (trade name manufactured by Shell Japan Co., Ltd .: 200 ° C. MFR (5 kg load) = 7 g / 10 minutes, styrene content 13% by mass, “Clayton” Is a registered trademark), Tuftec H1052 (Asahi Kasei Chemicals Corporation product name: 200 ° C. MFR (5 kg load) = 10 g / 10 min, styrene content 20% by mass, “Tuftec” is a registered trademark), Septon 2002 (Kuraray Co., Ltd.) Product name: 200 ° C. MFR (10 kg load) = 100 g / 10 min, styrene content 30% by mass, “Septon” is a registered trademark) and the like.

  Content of the hydrogenated styrene block copolymer (A) in a hot-melt resin composition is 5-30 mass% normally with respect to the whole hot-melt resin composition, Preferably it is 10-20 mass%. When the content is less than 5% by mass, the viscosity of the hot melt adhesive becomes low, and there is a possibility that a continuous coating pattern cannot be formed in a spiral shape. On the other hand, when it exceeds 30% by mass, the viscosity of the hot melt adhesive becomes high, and there is a possibility that problems such as clogging of the spray nozzle may occur.

The polybutene (B) in the hot melt resin composition used preferably has a kinematic viscosity at 100 ° C. of 10 to 2,000 mm ² / s, and the polybutene (B) has a normal double bond. Or a compound obtained by adding hydrogen to a double bond by hydrogenation and saturating it.
Content of polybutene (B) is 20-40 mass% normally with respect to the whole hot-melt resin composition, Preferably it is 25-35 mass%. When the content is less than 20% by mass, the viscosity of the pressure-sensitive adhesive is increased, tackiness is lowered, and workability at the time of application may be deteriorated. On the other hand, when it exceeds 40 mass%, the viscosity and adhesive force of the hot melt resin composition are remarkably lowered, and the heat resistance may be lowered.

When the 100 ° C. kinematic viscosity of the polybutene (B) is 10 to 2,000 mm ² / s, an effect of improving the compatibility with the hydrogenated styrene block copolymer (A) can be expected.
The 100 ° C. kinematic viscosity is a kinematic viscosity obtained by JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity pour point test method and viscosity index calculation method”.

Polybutene Examples of commercially available (B), polybutene 30 N (NOF Corporation, trade name, 100 ° C. kinematic viscosity; 700mm ² / s), polybutene 10 N (manufactured by NOF Corporation trade name, 100 ° C. kinematic viscosity; 280 mm ² / S).

As the tackifier resin (C) contained in the hot melt resin composition to be used, those having a softening point of 85 to 125 ° C. by the ring-and-ball method are preferable, and hydrogenated ones are particularly preferable. When the softening point is 85 to 125 ° C., there is an effect of improving the heat resistance creep resistance between the adherends of the laminated member. In general, the hydrogenated state is a state in which the number of double bonds between carbon and carbon in the molecular chain is 10% or less of the total, and further between carbon and carbon in the molecular chain. The number of double bonds is preferably 1% or less of the whole.
The softening point by the ring and ball method can be measured using, for example, a Meitec ring and ball automatic softening point tester ASP-M4 in accordance with JIS K2425.

  Examples of the tackifier resin (C) include aromatic petroleum resins, aliphatic petroleum resins, aliphatic-aromatic petroleum resins, terpene petroleum resins, rosin resins, modified terpene resins, modified rosin resins, and styrene. Examples of such petroleum petroleum resins include hydrogenated tackifying resins, which are resins obtained by hydrogenating the above-mentioned tackifying resins (C), and are two carbon atoms in the molecular chain. By reducing the number of double bonds, it means that the degree of oxidative deterioration mainly during heat melting or long-term use is reduced. These adhesion-imparting agents may be used alone or in combination of two or more. Furthermore, as the tackifier resin (C), a dicyclopentadiene polymer and a copolymer of dicyclopentadiene and a styrene derivative (including styrene) are particularly preferable, and these may be used alone or in two types. You may use together.

  Commercially available tackifying resins (C) include Clearon P100 (hydrogenated terpene resin, softening point: 100 ° C., trade name manufactured by Yasuhara Chemical Co., Ltd., “Clearon” is a registered trademark), Clearon P125 (hydrogenated terpene resin, softened) Point: 125 ° C., Yashara Chemical Co., Ltd., “Clearon” is a registered trademark), Alcon P100 (alicyclic hydrogenated petroleum resin, softening point: 100 ° C., Arakawa Chemical Industries, Ltd., “Arcon” And Alcon P90 (alicyclic hydrogenated petroleum resin, softening point: 90 ° C., trade name of Arakawa Chemical Industries, Ltd., “Arcon” is a registered trademark), and the like.

  20-70 mass% is preferable and, as for content of tackifying resin (C) in the hot-melt resin composition used, 30-60 mass% is more preferable. If it is less than 20% by mass, sufficient adhesion and tackiness cannot be obtained, and if it exceeds 70% by mass, the obtained hot-melt resin composition becomes hard and damages the adherend by pressure bonding at the time of bonding. There are problems such as.

  Furthermore, the hot-melt resin composition used includes a release agent such as a higher fatty acid and a higher fatty acid metal salt, a coupling agent, a stress relaxation agent such as silicone oil or silicone rubber powder, carbon black, etc., if necessary. An appropriate amount of a pigment or dye, an antioxidant (anti-aging agent), an ultraviolet absorber, a surfactant, a non-halogen, a non-antimony flame retardant, or the like may be blended.

  Examples of the antioxidant (anti-aging agent) include phenol, organic sulfur, hindered phenol, hindered amine, organic phosphorus hindered phenol, and amine. For example, pentaerythriyltetrakis-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate (SONGNOX1010, trade name of SONGWON IND.) And n-octadecyl-3 are used as phenolic antioxidants. -(3,5-di-tertiarybutyl-4-hydroxyphenyl) propionate (SONGNOX1076, product name manufactured by SONGWON IND.) And tris (2,4-di-tertiarybutylphenyl) as a phosphorus-based antioxidant Phosphite (SONGNOX 1680, product name made by SONGWON IND.) And the like. The content of the antioxidant (anti-aging agent) is preferably 0.1 to 2% by mass and more preferably 0.5 to 1% by mass with respect to the hot melt resin composition. When the content is less than 0.1% by mass, there is a risk of thermal degradation when the hot melt resin composition is heated and melted.

  The hot melt resin composition to be used can be prepared by any method as long as various raw materials can be uniformly dispersed and mixed. However, as a general method, raw materials of a predetermined blending amount are sufficiently mixed by a mixer or the like. Then, a method of mixing or melt-kneading with a mixing roll, an extruder, a raking machine, a planetary mixer, etc., and defoaming as necessary can be mentioned.

The hot-melt resin composition used preferably has a softening point of 80 to 120 ° C, more preferably 90 to 110 ° C. When the softening point of the hot-melt resin composition is less than 80 ° C., the heat resistance characteristics are insufficient, and when it exceeds 120 ° C., the solidification time is shortened and workability may be reduced.
The softening point can be measured, for example, according to JIS K2425 using a ring and ball automatic softening point tester ASP-M4 manufactured by Meitec Co., Ltd.

The hot melt resin composition used has a melt viscosity of preferably 2,500 to 5,500 mPa · s, more preferably 3,000 to 5,000 mPa · s at 160 ° C. If the melt viscosity of the hot-melt resin composition is less than 2,500 mPa · s, the continuity of the hot-melt resin during spraying may be lost, and if it exceeds 5,500 mPa · s, the sprayability deteriorates due to high viscosity. There is a risk.
The melt viscosity at 160 ° C. is, for example, 10 minutes after curing at 160 ° C. for 10 minutes using a B type small-scale viscometer (measurement part: TV-20, heater part: VTB-250) manufactured by Toki Sangyo Co., Ltd. The value after rotating for a minute can be taken as the melt viscosity.

The hardness (Shore C) of the hot-melt resin composition used is preferably 4 to 16, more preferably 5 to 14, at 23 ° C. When the hardness (Shore C) is in the range of 4 to 16, the effect of suppressing damage to the adherend can be obtained.
The hardness (Shore C) at 23 ° C. can be measured in a 23 ° C. environment using, for example, a Shore C hardness meter manufactured by Teclock Corporation.

  EXAMPLES Examples and comparative examples according to the present invention will be described below, but the present invention is not limited to the examples.

(Examples 1-4, Comparative Examples 1-2)
A hot melt resin composition was prepared according to the formulation shown in Table 1. A heating kneader having an internal volume of 1 L was used for this preparation. It put into the heating kneader set to 180 degreeC so that the total compounding quantity of each component might be 500 g, and it was fully fuse | melted. Then, it knead | mixed until the resin composition became uniform. After kneading sufficiently, the molten resin composition was taken out and cooled and solidified at room temperature (25 ° C.).
About the obtained hot-melt resin composition, melt viscosity, softening point, Tanδ, hardness, and thermal stability were evaluated by the methods shown below. The results are shown in Table 2.

（配合単位；質量部）
クレイトンＧ１６５７；シェルジャパン株式会社製商品名、スチレン−エチレン− ブチレン−スチレンブロック共重合体ゴム、スチレン含有量１３質量％、ＭＦＲ＝７（２００℃）
タフテックＨ１０５２；旭化成ケミカルズ株式会社製商品名、スチレン−エチレン−ブチレン−スチレンブロック共重合体ゴム、スチレン含有量２０質量％、ＭＦＲ＝２０（２００℃）
セプトン２００２；クラレ株式会社製商品名、スチレン−エチレン− プロピレン−スチレンブロック共重合体ゴム、スチレン含有量３０質量％、ＭＦＲ＝１００（２００℃）
ポリブテン３０Ｎ；日本油脂株式会社製商品名、１００℃動粘度＝７００ｍｍ^２／ｓ
ポリブテン１０Ｎ；日本油脂株式会社製商品名、１００℃動粘度＝２８０ｍｍ^２／ｓ
クリアロンＰ１００；ヤスハラケミカル株式会社製商品名、水添テルペン樹脂、軟化点１００℃
クリアロンＰ１５０；ヤスハラケミカル株式会社製商品名、水添テルペン樹脂、軟化点１５０℃
ＪＣＴオイルＢ；ジャパンケムテック株式会社製商品名、プロセスオイル

(Blend unit; parts by mass)
Clayton G1657; trade name, manufactured by Shell Japan Co., Ltd., styrene-ethylene-butylene-styrene block copolymer rubber, styrene content 13% by mass, MFR = 7 (200 ° C.)
Tuftec H1052; trade name of Asahi Kasei Chemicals Corporation, styrene-ethylene-butylene-styrene block copolymer rubber, styrene content 20% by mass, MFR = 20 (200 ° C.)
Septon 2002; trade name, manufactured by Kuraray Co., Ltd., styrene-ethylene-propylene-styrene block copolymer rubber, styrene content 30% by mass, MFR = 100 (200 ° C.)
Polybutene 30N; trade name of Nippon Oil & Fat Co., Ltd., 100 ° C. kinematic viscosity = 700 mm ² / s
Polybutene 10N; trade name of Nippon Oil & Fat Co., Ltd., 100 ° C. kinematic viscosity = 280 mm ² / s
Clearon P100; trade name of Yashara Chemical Co., Ltd., hydrogenated terpene resin, softening point 100 ° C
Clearon P150; Yasuhara Chemical Co., Ltd. trade name, hydrogenated terpene resin, softening point 150 ° C
JCT Oil B; Japan Chemtech Co., Ltd. trade name, process oil

[Melt viscosity]
Using a B-type small-scale viscometer manufactured by Toki Sangyo Co., Ltd. (measurement part: TV-20, heater part: VTB-250), after curing at 160 ° C. for 10 minutes, the value after rotating for 10 minutes is taken as the melt viscosity. It was measured. The results are shown in Table 2.
[Softening point]
Based on JIS K2425, the softening point was measured with Meitec Co., Ltd. ring-and-ball type automatic softening point tester ASP-M4. The hot melt resin composition used for the softening point test was dissolved in advance at 180 ° C., poured into a ring for softening point test, and solidified before being used for air cooling for one day. The results are shown in Table 2.
[Tanδ]
The Tan δ value at 80 ° C. was measured using a rheometer AR2000ex manufactured by TA Instruments. The measurement conditions are a measurement temperature of 80 ° C. and a frequency of 1 to 10 Hz. The results are shown in Table 2. In Table 2, “◯” indicates a case where the Tan δ value is 0.2 to 1.0, and “x” indicates a case where 1.0 is exceeded.
[Hardness]
The hot-melt resin composition is cured for 2 hours or more in an environment of 23 ° C., and the hardness is measured by pressing a smooth portion of the resin composition for 5 seconds using a Shore C hardness meter (manufactured by Technoc), and evaluated according to the following criteria. did. The results are shown in Table 2.
“◯”: Good, Shore C hardness (23 ° C.) = 4 to 16
“X”; unsuitable, Shore C hardness (23 ° C.) = Less than 4 or more than 16 [thermal stability]
70 g of the hot melt resin composition was placed in a 250 ml mayonnaise bottle and left in a 180 ° C. dryer for 120 hours. The change of the state at this time was observed and evaluated according to the following criteria. The results are shown in Table 2.
“○”: No change in state “×”: Generation of gelled and carbides

The hot melt resin compositions obtained in Examples 1 to 4 and Comparative Examples 1 and 2 were applied to one side of a 170 μm thick PP film (polypropylene film) as an adherend using a Nordson summit spray. : Applied at about 50 g / m ² , applicator temperature (gun part 170 ° C., hose part 140-160 ° C., melter part 140-160 ° C.), application distance 20 mm, and coating speed of adherend 12 m / min.
[Spray application state]
The spray coating pattern and the damage (wrinkle, shrinkage) to the adherend when the hot melt resin composition was applied using a summit spray were visually confirmed. The results of evaluation according to the following criteria are shown in Table 2.
“◯”: A regular spiral coating pattern is formed, the coating amount is constant, and no damage to the adherend occurs.
"X": The coating pattern is irregular and discontinuous, the coating amount is uneven, and damage to the adherend occurs.

(Production of laminated member and evaluation of adhesiveness)
A fibrous hot melt resin composition is applied to a portion of 25 mm wide × 25 mm long on two PP films (adhered body) having a thickness of 170 μm × width 25 mm × length 75 mm. The parts coated with the resin composition were overlapped, and a pressure of 0.15 MPa was applied for about 5 seconds at room temperature (25 ° C.) to produce a laminated member.
The laminated member was treated at a temperature of 50 ° C. and a humidity of 95% for 0 hour (initial state), 168 hours, 480 hours, and 720 hours, and the shear strength of the laminated member was measured.
As a method for measuring the shear strength, the laminated member was pulled in the shear direction at a pulling speed of 500 mm / min at room temperature (25 ° C.) using an autograph IS-5000 manufactured by Shimadzu Corporation, and the maximum load was applied. Was measured (see FIG. 2).
As the adhesiveness, the number of samples was five, the shear strength of the laminated member was 0.15 MPa or more as good “◯”, and the one less than 0.15 MPa was judged as “bad”.
The evaluation results of the adhesiveness of the laminated member are shown in Table 2.

As shown in Table 2, Examples 1-4 of the present invention have Tan δ, hardness (Shore C), etc. within an appropriate range, and are excellent in thermal stability, spray application state, and adhesiveness. I understand that.
On the other hand, it turns out that the comparative examples 1-2 whose Tan (delta) exceeds 1.0 have a problem in a spray application state or adhesiveness.
According to the present invention, the occurrence of carbides during heating is suppressed, the adhesive properties and hydrolysis resistance are excellent, and even the adherend that is weak against heat has very little damage to the adherend, and the adhesive surface is kept smooth. It became possible to provide the manufacturing method of the hot-melt resin composition which can be bonded together by this, and the laminated member using the same.

1: adherend, 2: hot melt resin composition, 3: PP film (adherence) 4: shear direction.

Claims (7)

  A method for producing a laminated member formed by bonding a plurality of adherends including at least one adherend having an allowable heating temperature of 80 ° C. or less, wherein Tan δ measured by a rheometer at 80 ° C. is 0.2. A method for producing a laminated member in which a hot melt resin composition of -1.0 is applied to an adherend, and then overlapped and adhered to the adherend. The hot melt resin composition comprises a hydrogenated styrene block copolymer (A), a polybutene (B) having a kinematic viscosity at 100 ° C. of 10 to 2,000 mm ² / s, and a softening point of 85 to 125 ° C. by the ring and ball method. The manufacturing method of the laminated member of Claim 1 containing a certain tackifier resin (C).   The tackifier resin (C) is a hydrogenated tackifier resin and is at least one of a dicyclopentadiene polymer and a copolymer of dicyclopentadiene and a styrene derivative (including styrene). The manufacturing method of the laminated member of 2.   The method for producing a laminated member according to claim 2 or 3, wherein the hot-melt resin composition has an oil component content of 5 mass% or less.   The manufacturing method of the laminated member in any one of Claim 1 to 4 with which the tangent vector with respect to the application | coating locus | trajectory of the hot-melt resin composition apply | coated to the to-be-adhered body shows 360 degree directionality.   The method for producing a laminated member according to any one of claims 1 to 5, wherein an application locus of the hot melt resin composition applied to the adherend is a spiral shape. It is a hot-melt resin composition used for the manufacturing method of the laminated member in any one of Claim 1 to 6, Comprising: A hydrogenated styrene block copolymer (A) and 100 degreeC kinematic viscosity are 10-2,000 mm < ² >. / S polybutene (B) and a hot-melt resin composition containing a tackifier resin (C) having a softening point of 85 to 125 ° C. by the ring and ball method.

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