KR20080113390A - Adhesive material, method for production of the adhesive material, and method for production of adhered article or laminate using the adhesive material - Google Patents

Abstract

Disclosed is an adhesive material for multi-layer coextrusion, wherein the adhesive material comprises a mixture of the following particles (A), (B) and (C): (A) a particle comprising a rubbery block copolymer (1a) and an adhesiveness-imparting resin (2), wherein the rubbery block copolymer (1a) comprises mainly a styrene block and a diene block; (B) a particle comprising a rubbery block copolymer (1b) and a plasticizer (3), wherein the rubbery block copolymer (1b) comprises mainly a styrene block and a diene block; and (C) a particle comprising a rubbery block copolymer (1c) which comprises mainly a styrene block and a diene block. ® KIPO & WIPO 2009

Description

Adhesive material, its manufacturing method, and the manufacturing method of the adhesive substance and laminated body using the same {ADHESIVE MATERIAL, METHOD FOR PRODUCTION OF THE ADHESIVE MATERIAL, AND METHOD FOR PRODUCTION OF ADHERED ARTICLE OR LAMINATE USING THE ADHESIVE MATERIAL}

This invention relates to the adhesive material used for manufacture of the adhesive substance used for the adhesive layer of an adhesive tape, a multilayer body, etc., and its manufacturing method.

Conventionally, a method of forming a pressure-sensitive adhesive layer by volatilizing an organic solvent after dissolving it in an organic solvent and coating it as a pressure-sensitive adhesive material has been performed. That is, it is known to heat and melt-extrude an adhesive material, to coat | cover a base material, to manufacture an adhesive tape (patent document 1), or to set it as the packaging material which can be resealed by the coextrusion method (patent document 2).

As an adhesive material, as shown in patent document 1, tackifying resins, such as a terpene resin and a petroleum resin, ethylene-vinyl acetate copolymer, a vinyl chloride copolymer, or a styrene rubbery copolymer, liquid paraffin, synthetic wax, There is what mix | blended plasticizers, such as process oil.

However, since these adhesive materials are adhesive, they cannot be used unless they are mixed with a twin screw extruder or other kneader. If a twin-screw extruder is provided, it is possible to coat the substrate, extrude lamination or co-extrusion with other resins, and the adhesive material has a strong re-adhesive strength. There is a drawback that is limited.

On the other hand, in patent document 2 and patent document 3, what mix | blended tackifying resin with the styrene rubbery copolymer is shown as an adhesive material.

Although these raw materials can be extruded with a uniaxial material, since the tackifying resin is weak and many have a softening point of 150 ° C. or lower, debris of the tackifying resin adheres to the screw grooves in the lower part of the extruder hopper to form grooves. The buried or heatd melts it into an oily phase to smooth the resin, causing extrusion fluctuations.

Moreover, since plasticizers, such as liquid paraffin, synthetic wax, and process oil, are not mix | blended, there existed a problem that re-adhesion strength was weak.

Patent Document 1: Japanese Patent Application Laid-open No. 55-139477

Patent Document 2: Japanese Unexamined Patent Publication No. 2003-175567

Patent Document 3: Japanese Patent Application Laid-Open No. 07-224255

This invention is made | formed in view of the above-mentioned problem, and an object of this invention is to provide the adhesive material with strong re-adhesion strength extruded with a single screw extruder.

Disclosure of the Invention

According to this invention, the following adhesive materials etc. are provided.

1. The adhesive material for multilayer coextrusion in which the following particle | grains (A), (B), and (C) are mixed.

(A) Particles consisting mainly of a rubbery block copolymer (1a) containing a styrene block and a diene block and a tackifying resin (2)

(B) Particles composed mainly of a rubbery block copolymer (1b) and a plasticizer (3) containing styrene blocks and diene blocks

(C) Particles mainly consisting of rubbery block copolymer (1c) containing styrene blocks and diene blocks

2. The adhesive material for multilayer coextrusion of 1 whose following component is contained in the following compounding quantity.

40-70 weight% of rubbery block copolymers (1) which combined the said rubbery block copolymer (1a), (1b), and (1c)

Said tackifying resin (2): 20-50 weight%

Plasticizer (3): 10 to 30% by weight

3. The adhesive material for multilayer coextrusion of 2 whose following component is contained in the following compounding quantity.

Rubber block copolymer (1) which combined said rubber block copolymer (1a), (1b), and (1c): 50-55 weight%

Said tackifying resin (2): 24-30 weight%

Plasticizer (3): 18-21 wt%

4. Melt-mixing the rubbery block copolymer (1a) mainly containing a styrene block and a diene block, and the tackifying resin (2), granulates the particle (A),

The rubbery block copolymer (1b) mainly containing a styrene block and a diene block, and the plasticizer (3) are melt-blended to assemble the particle (B),

The rubbery block copolymer (1c) containing mainly styrene blocks and diene blocks is melted to assemble the particles (C),

The manufacturing method of the adhesive material for multilayer coextrusion of 1 which dry-blends the said particle | grain (A), the said particle | grain (B), and the said particle | grain (C).

5. The manufacturing method of the laminated body which consists of an adhesion layer and resin layer which melt-knead the adhesive material for multilayer coextrusion as described in any one of 1-3 in coaxial extrusion with resin, and a resin.

6. Manufacturing method of multilayer body which melt-bonds the laminated body manufactured by 6. to a base material.

ADVANTAGE OF THE INVENTION According to this invention, the adhesive material with strong resticking strength extruded with a single screw extruder can be provided.

Implement the invention  Best form for

The adhesive material of this invention mixes and contains the following particle | grains (A), (B), (C).

(A) Particles consisting mainly of a rubbery block copolymer (1a) containing a styrene block and a diene block and a tackifying resin (2)

(B) Particles composed mainly of a rubbery block copolymer (1b) containing a styrene block and a diene block and a plasticizer (3)

(C) a rubbery block copolymer mainly containing styrene blocks and diene blocks (1c)

The rubbery block copolymers (1a), (1b) and (1c) containing a styrene block and a diene block also contain a hydrogenated block copolymer hydrogenated product containing a styrene block and a diene block. For example, a block copolymer in which a polystyrene block and a vinyl-polyisoprene block are combined, a block copolymer in which a polystyrene block and an ethylene-propylene block are combined, a block copolymer in which a polystyrene block and an ethylene butadiene block are combined, a polystyrene block and an ethylene And a block copolymer in which an ethylene-propylene block is bonded. Preferably, it is a rubbery block copolymer hydrogenated substance in that there is no odor.

In addition, the rubber block copolymer 1a and the rubber block copolymer 1b may be the same or different. The rubbery block copolymer (1c) may be the same as or different from the rubbery block copolymers (1a) and (1b). However, the rubbery block copolymer (1c) is preferred because it is easy to adjust physical properties.

In addition, the rubber block copolymers (1a), (1b) and (1c) of the present invention may be granulated by adding an antioxidant, a lubricant, and the like in advance within the range of not impairing their properties.

As tackifying resin (2), hydrogenated rosin-type resin, terpene-type resin, hydrogenated terpene-type resin, C5 * C6 system aliphatic petroleum resin, alicyclic petroleum resin, etc. are mentioned, for example.

In particle | grains (A), it is preferable to mix | blend a tackifying resin normally at 40 weight% or more and 90 weight% or less. When the tackifying resin is less than 40% by weight, the granules are sticky, and when the amount exceeds 90% by weight, the granules are weak and debris may adhere to the screws.

Examples of the plasticizer (3) include liquid paraffin, process oil (aromatic or naphthenic or paraffinic petroleum monovalent hydrogen), synthetic wax, and the like.

In particle | grains (B), the compounding quantity of a plasticizer is normally 40 weight% or more and less than 75 weight% in order to ensure extrusion stability. When the compounding amount is less than 40% by weight, control ranges such as cutability of the pressure-sensitive adhesive material obtained, slip sticking property of peeling are narrowed, and the kneading becomes uneven at 75% by weight or more.

When the adhesive material of this invention is added to the said particle | grains (A) and (B), and further mixing the following particle | grains (C), the compounding ratio of a rubbery block copolymer, tackifying resin, and a plasticizer can be adjusted, and an adhesive material It is preferable in that the physical properties can be changed according to the requirements of. Specifically, since particle | grains (C) can be added separately, the compounding ratio of the adhesive material itself can be adjusted more easily and extensively. Moreover, by adding particle | grain (C), the compounding ratio of each component of particle | grains (A) and (B) can be adjusted so that granulation becomes easy, and the kind of each component of particle | grains (A) and (B) You can choose from a wide range. In addition, by adding the particles (C), the viscosity can be adjusted at the time of coextrusion, the multilayers can be arranged, and the formation of the multilayers is facilitated.

The adhesive material of this invention is a rubbery block copolymer (1) which combined all the rubbery block copolymer (1) contained in an adhesive material, ie, said rubbery block polymer (1a), (1b), and (1c), and tackifying resin. Preferably the compounding quantity of (2) and the plasticizer (3) is 40-70 weight% 20-50 weight%: 10-30 weight%, More preferably, 40-60 weight%: 22-50 weight%: 10- 28 wt%.

When the compounding quantity of (1), (2), and (3) is out of the said range, there exists a possibility that rebonding strength may weaken.

In particular, the adhesive material containing 50-55 weight% of rubbery block copolymers (1), 24-30 weight% of tackifying resins (2), and 18-21 weight% of plasticizers (3) is a novel adhesive material.

The adhesive material of this invention can be produced by the following manufacturing methods, for example.

The particle | grains (A) are granulated by melt-mixing the rubbery block copolymer (1a) and tackifying resin (2) which mainly contain a styrene block and a diene block. On the other hand, the rubbery block copolymer (1b) and the plasticizer (3) mainly containing a styrene block and a diene block are melt-blended to assemble the particle (B). Further, the rubbery block copolymer (1c) mainly containing styrene blocks and diene blocks is melted to assemble the particles (C). Thereafter, particles (A), particles (B), and particles (C) are dry blended.

Particles (A) are obtained by granulating the rubber block copolymer (1a) and the tackifying resin (2) with a twin screw extruder or a Banbury mixer.

If the granulated material is sticky, a lubricant such as talc powder may be appropriately blended into the granulated material in order to prevent blocking. Fillers, antioxidants, coloring agents and the like are added as necessary during granulation.

Particles (B) are obtained by assembling the rubber block copolymer (1b) and the plasticizer (3) with a twin screw extruder or Banbury mixer or the like.

When the granulated material is sticky, a lubricant such as talc powder may be appropriately blended into the granulated material in order to prevent blocking. Fillers, antioxidants, coloring agents and the like are added as necessary during granulation.

About particle | grains (C), you may granulate the rubber block copolymer 1c by adding a peeling strength modifier, a filler, antioxidant, a coloring agent, etc. beforehand.

Since the adhesive material of this invention mixes the above particle | grains (A), (B), (C), it is hard to adhere to the hopper of an extruder, and can be melt-kneaded with a single screw extruder. The adhesive material of this invention can be extruded and made into an adhesive.

In addition to the single screw extruder, the extruder may be a twin screw extruder, a kneader or the like.

The adhesive material of this invention can be preferably used especially for multilayer coextrusion.

As extrusion molding, co-extrusion, extrusion coating, and extrusion lamination are mentioned, for example.

Co-extrusion means, for example, three or more layers of coextrusions using an adhesive material such as a resin layer / adhesive material / resin layer as an intermediate layer, or two or more layers of coextrusions using an adhesive material such as a resin layer / adhesive material as a single layer. Say The resin layer is made of polyolefin or the like.

In extrusion coating, for example, paper, a synthetic resin film (polyethylene terephthalate (PET), ethylene-vinyl alcohol copolymer (EVOH), metaxylenediamine (MXD) nylon, polypropylene (PP), polyethylene (PE), nylon) and a nonwoven fabric as a base material, and an adhesive material is coated on the base material.

In extrusion lamination, for example, melt-extrusion of the adhesive material between two kinds of films selected from paper, a synthetic resin film (PET, EVOH, MXD nylon, PP, PE, nylon, etc.), nonwoven fabric, or a film in which they are laminated. 2 types are compressed and laminated | stacked.

The multilayer body can be obtained by melt-bonding the adhesive substance obtained by extrusion molding the adhesive material of this invention, or the laminated body which consists of an adhesion layer and a resin layer obtained by coextrusion to a base material. The above-mentioned thing can be used as a base material.

From the multilayer body containing the adhesion layer which consists of a fixing material of this invention, and the member adhere | attached to this multilayer body, the opening or closing part of a package or at least a package can be comprised. When the multilayer body or the adhesive member is peeled off, the multilayer body is broken and the adhesive layer is exposed. The package can be resealed by fitting the fracture portion back to the exposed adhesive layer.

EXAMPLE

Hereinafter, the present invention will be described in more detail with reference to Examples.

[Assessment Methods]

Evaluation of the obtained sample was performed by the following method.

(I) Extrudeability: It was confirmed that there was no problem by checking screw contamination under the surging or the hopper, and it was judged that any defect phenomenon was observed as defective.

(II) Re-adhesive strength: Polyethylene terephthalate (PET) (12 µm) / linear low density polyethylene (L-LDPE) (60 µm) laminate with respect to the high density polyethylene (HDPE) side of the produced three-layer multilayer film The film was pressed by pressing a heat seal tooth from a PET side at a surface pressure of 190 ° C. 2 Mpa, and bonding was performed by performing a heat seal having an area of 50 mm × 50 mm. Next, after slitting to a width of 15 mm, it was once squeezed out by hand, and the re-adhesive strength after pressurizing by hand was measured by a push-pull scale (MX-500N manufactured by Imada Co., Ltd.). 1N / 15mm-less than 2N / 15mm were possible as a criterion of the acceptance judgment, 2N / 15mm-less than 3N / 15mm were favorable, and 3N / 15mm or more was the best. Moreover, less than 1 N / 15 mm was made impossible.

Example 1

[Production of particulate adhesive material]

(1) Kneading granulation of rubber block copolymer (hereinafter abbreviated as styrene-based elastomer) containing styrene block and diene block and tackifying resin (particle (A1))

Polystyrene-polyisoprene block copolymer (Nippon Xeon Co., Ltd., Quintech 3520) (MFR = 7 g / 10 min (200 ℃, load 5 kg), specific gravity 0.93) to 25% by weight of C5- aromatic copolymer hydrogenated resin To 100 parts by weight of 75 parts by weight of particles (Idemitsu Heungsan Co., Ltd., IMAB P-125) (softening point 125 ° C, density 1.03 g / cm 3 (20 ° C)), an antioxidant (Chiba Specialty Chemicals Co., Ltd.) Note) 1 part by weight of Irganox 1010) was added and stirred and mixed. Thereafter, the mixture was melt mixed at a temperature of 180 ° C. with a twin screw extruder, followed by water cooling strand extrusion, and further cut and granulated.

(2) Kneading Assembly of Styrene-Based Elastomer and Plasticizer (Particle (B1))

Polystyrene-polyisoprene block copolymer (manufactured by Nippon Xeon Co., Ltd., Quintaq 3520) (MFR = 7 g / 10 min (200 ° C., load 5 kg), specific gravity 0.93) to 40 wt% of process oil (Idemitsu Heungsan Co., Ltd.) 60 wt% of Manufacture, Diana Process Oil PW-90 (density 0.8722 g / cm 3 (15 ° C.)) was added, stirred and mixed, followed by melt mixing at a temperature of 180 ° C. using a twin screw extruder, followed by water-cooled strand extrusion. Cut and assembled.

In the granulated product, 0.5 parts by weight of talc powder was added to 100 parts by weight of the granulated powder to prevent blocking of particles during packing.

(3) Mixing of Particles (A1), (B1), and (C1)

Styrene-based rubber block copolymer particles (Nippon Xeon Co., Ltd., Quintech SL-125) (MFR = 17 g / 10 min (200 ° C, load 5 kg), specific gravity 0.93) to the particles (A1) and particles (B1). (C1) was added and mixed to prepare an adhesive material. The blending ratio of the styrene-based elastomer, the tackifying resin, and the plasticizer was 50.8 wt%: 30.0 wt%: 19.2 wt%.

[Co-Extrusion of Adhesive Materials]

HDPE (manufactured by Prime Polymer Co., Ltd., HiJex 110J) (MFR = 12 g / 10 min, density 0.962 g / cm 3), adhesive material obtained above and random polypropylene (RPP) (manufactured by Prime Polymer Co., Ltd., prime poly Pro F-744NP) (MFR = 6.4 g / 10 min, density 0.9 g / cm 3), three 30 mm diameter single screw extruders with full-flight screws with L / D = 26, multilayer feed block and T die (width It extruded at 220 degreeC using the multilayer film cast manufacturing apparatus which consists of 400 mm), and produced three layers of multilayer films. The thickness of the film was set to HDPE layer 10 µm / adhesive layer 20 µm / RPP layer 50 µm. The adhesive material could be extruded smoothly for a long time. The results are shown in Table 1.

Comparative Example 1

To 32% by weight of the particles (B1) used in Example 1, C5-aromatic copolymer-hydrogenated resin particles (Idemitsu Heungsan Co., Ltd., Imab P-125) (125 ° C softening point, density 1.03 g / cm 3 (20 ° C) )) Is added 30% by weight, and by further mixing 38% by weight of SL-125 as styrene-based elastomer particles, the ratio of styrene-based elastomer: tackifying resin: plasticizer is 50.8% by weight: 30.0% by weight: 19.2% by weight It was.

A film was produced in the same manner as in Example 1 except that the above adhesive material was used. After starting extrusion, the extrusion amount of the pressure-sensitive adhesive layer began to fluctuate after a while.

When this extruder was stopped and the screw contamination under the hopper was confirmed, it turns out that the petroleum resin softened and adhered to the screw groove, and the extrusion failure occurred. The results are shown in Table 1.

In Comparative Example 1, the sample could not be collected, and thus the re-adhesion strength was not evaluated.

Example 2-14

The particles (A1), particles (B1), and particles (C1) used in Example 1 were blended so that the ratio of styrene-based elastomer: tackifying resin: plasticizer was the same as in Table 1, and the film was prepared in the same manner as in Example 1. The same evaluation was performed as it prepared. The results are shown in Table 1.

Comparative Example 2-5

In the same manner as in Example 1, the SL-125 particles were blended with the particles (A1) used in Example 1 so that the ratio of styrene-based elastomer: tackifying resin: plasticizer was as in Table 1. The same evaluation was performed. The results are shown in Table 1.

Example 15-17

The particle | grains were manufactured like Example 1 except having changed the compounding ratio of the styrene-type elastomer of particle | grain (A1) and tackifying resin as shown in Table 2. The particles were packed in bags of 20 kg each to evaluate blocking between pellets after two weeks of storage. The results are shown in Table 2.

Example 18-20

The particle | grains were manufactured like Example 1 except having changed the compounding ratio of the styrene-type elastomer of particle | grain (A1) and tackifying resin as shown in Table 2. It evaluated like Example 15-17. The results are shown in Table 2.

Example 21

The pressure-sensitive adhesive material prepared in Example 1 was attached to a 40 mmφ single-flight screw (L / D = 28) extruder with a T die having a width of 500 mm, and an extrusion laminator for pressing the extruded melt web into two rolls of rubber rolls and cooling metal rolls. Both sides of the melt web and the silicone coat process paper (the coat side is the melt web side) were reported. The configuration was printing paper (150 g / m 2) / adhesive layer (20 μm) / process paper (100 g / m 2).

After cutting the laminated 3-layer sheet to 140 mm x 210 mm, process paper was peeled off and the adhesive surface was affixed on glass, and it was left to stand at 23 degreeC of environment temperature for 2 weeks. The adhesion state was good, and the period during the adhesion was not peeled off, and when peeled off after 2 weeks, it could be easily peeled off without leaving a paste.

The fixing material of this invention can be used suitably as industrial materials, such as a poster, an adhesive tape, a label, and packaging materials, such as a resealed foodstuff, pharmaceutical packaging material, and a protective film.

Claims (6)

The adhesive material for multilayer coextrusion which the following particle | grains (A), (B), (C) are mixed. (A) Particles consisting mainly of a rubbery block copolymer (1a) containing a styrene block and a diene block and a tackifying resin (2) (B) Particles composed mainly of a rubbery block copolymer (1b) containing a styrene block and a diene block and a plasticizer (3) (C) Particles composed mainly of the rubbery block copolymer (1c) containing styrene blocks and diene blocks. The method of claim 1, The adhesive material for multilayer coextrusion which the following component contains in the following compounding quantities. 40-70 weight% of rubbery block copolymers (1) which combined the said rubbery block copolymer (1a), (1b), and (1c) Said tackifying resin (2): 20-50 weight% Plasticizer (3): 10 to 30% by weight The method of claim 2, The adhesive material for multilayer coextrusion which the following component contains in the following compounding quantities. Rubbery block copolymer (1) which combined the said rubbery block copolymer (1a), (1b), and (1c): 50-55 weight% Said tackifying resin (2): 24-30 weight% Plasticizer (3): 18-21 wt% The method of claim 1, The rubbery block copolymer (1a) mainly containing a styrene block and a diene block, and the tackifying resin (2) are melt-blended to granulate the particle (A), The rubbery block copolymer (1b) mainly containing a styrene block and a diene block, and the plasticizer (3) are melt-blended to assemble the particle (B), The rubbery block copolymer (1c) mainly containing styrene blocks and diene blocks is melted to assemble the particles (C), The manufacturing method of the adhesive material for multilayer coextrusion which dry-blends the said particle | grains (A), the said particle | grains (B), and the said particle | grains (C). The manufacturing method of the laminated body which consists of an adhesion layer and a resin layer which melt-knead the multilayer co-extrusion adhesive material in any one of Claims 1-3 with a single screw extruder, and coextrude with resin. The manufacturing method of the multilayer body which melt-bonds the laminated body manufactured in Claim 5 to the base material.