JP2008194932A - Laminate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To manufacture a laminate allowing coloration with titanium oxide and having improved releasability without a process of coating a silicone compound containing an organic solvent. <P>SOLUTION: A laminate employed has a layer (A) composed of an olefinic polymer containing 0.1-20 wt.% of titanium oxide and a layer (B) composed of a releasable resin composition comprising 93-99.99 wt.% of an olefinic polymer and 0.01-7 wt.% of a polydimethylsiloxane, laminated at least on one side of a substrate. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a laminate comprising a release film resin composition. More specifically, the present invention relates to a laminate that can be colored without impairing excellent releasability with respect to a pressure-sensitive adhesive or the like and that has excellent adhesion to a substrate.

  The release film is a film-like material provided with a release surface that is laminated on the adhesive surface to protect the adhesive surface of the adhesive material when not in use, and is easily peeled without damaging the adhesive surface when in use. Widely used as a mount for adhesive tapes and labels. The release film usually includes a base material and a release layer containing a release agent provided on at least one surface of the base material. Paper, plastic film, etc. are used for the base material, and a silicone compound, a long-chain alkyl group-containing compound, etc. are used for the release agent. In such a release film, when the release agent is not sufficiently adhered to the substrate, the release agent is transferred to the adhesive surface of the tape or label when the tape or label is peeled off from the release film. And the stickiness of the label may be deteriorated.

  For this reason, as a method for producing a release film, a method in which a release agent such as vinyl group-containing polydimethylsiloxane is coated on a substrate and then the release agent is cured is generally used. However, in this method, there are problems that a large amount of an organic solvent is used to uniformly apply the release agent, and that the base material is exposed to a high temperature when the release agent is cured, so that pinholes are generated. It was.

  For this reason, a method for imparting releasability to a plastic as a base material instead of a coating method has been proposed.

  Therefore, the present inventor, as a method of imparting releasability to the plastic as a base material instead of a method of coating, a resin composition containing a small amount of polydimethylsiloxane showing a specific epoxy equivalent to an olefin polymer, and A release film was proposed in which the surface of the olefin polymer was oxidized (see Patent Document 1).

  According to this method, the adhesion between the olefin polymer and polydimethylsiloxane is good, but when a pigment containing titanium oxide is added to the resin composition, the releasability is deteriorated and satisfactory performance cannot be obtained. The problem that occurred. Therefore, it is difficult to use a release film made of the resin composition as a substrate such as a cloth adhesive tape in which a material obtained by adding a pigment to an olefin polymer is generally used.

JP 2004-297398 A

  The present invention has been made in view of the above situation, and can be colored with titanium oxide without requiring a coating step of a silicone compound containing an organic solvent, and the releasability is improved. It is an object to provide a laminated body.

  As a result of intensive studies to solve the above problems, the present inventors have provided a layer made of an olefin polymer containing titanium oxide on at least one side of the substrate, and further, an olefin polymer and polydimethylsiloxane are provided on the layer. It has been found that a laminate having a layer made of is excellent in releasability from a pressure-sensitive adhesive and exhibits high adhesive strength with a substrate, and has completed the present invention.

That is, the present invention is a laminate characterized in that (A) layer satisfying the following requirements is laminated on at least one surface of the substrate, and (B) layer satisfying the following requirements is laminated on the (A) layer. It is about.
(A) Layer: A layer made of an olefin polymer containing 0.1 to 20% by weight of titanium oxide.
(B) Layer: A layer composed of a releasable resin composition composed of 93 to 99.99% by weight of an olefin polymer and 0.01 to 7% by weight of polydimethylsiloxane.

  In the present invention, the releasable resin composition used for the layer (B) is 100 parts by weight of a composition comprising 93 to 99.99% by weight of an olefin polymer and 0.01 to 7% by weight of polydimethylsiloxane. On the other hand, the present invention relates to a laminate comprising 0.001 to 1 part by weight of a curing catalyst containing tin and / or titanium in the molecule.

  The present invention also relates to a laminate in which the surface of the layer (B) is oxidized by at least one treatment method selected from corona discharge treatment, flame treatment, or plasma treatment.

  Furthermore, the present invention relates to a laminate in which the base material is one or more selected from paper, synthetic resin and / or natural material selected from woven fabric or non-woven fabric.

  The present invention is described in detail below.

  Examples of the substrate constituting the laminate of the present invention include a synthetic polymer film or sheet, woven fabric, nonwoven fabric, paper, metal foil and the like. Examples of the synthetic polymer film or sheet include a film or sheet made of a synthetic polymer such as polyester such as polyethylene terephthalate, polyamide, polyvinyl alcohol, saponified ethylene / vinyl acetate copolymer, polycarbonate, polyethylene, or polypropylene. Furthermore, these polymer films or sheets may have a surface deposited with aluminum, alumina, silica or the like, or may have a surface printed with urethane-based ink or the like. Examples of the woven fabric and non-woven fabric include those made of synthetic resin such as polyester, polyethylene, and polypropylene, or those made of natural materials such as sufu. Examples of the paper include craft paper, kulpack paper, high-quality paper, glassine paper, and paperboard. Among these, paper, or a woven or non-woven fabric made of a synthetic resin and / or a natural material is preferable because it is easy to cut the obtained laminate. In addition, an anchor coating agent such as an isocyanate compound, a urethane compound, or a polyethyleneimine compound may be applied to the surface of these base materials.

  The olefin polymer used in the (A) layer and the (B) layer of the present invention is a homopolymer of an α-olefin having 2 to 12 carbon atoms such as ethylene, propylene, 1-butene or a vinyl compound. Indicates coalescence. For example, low density polyethylene, high density polyethylene, ethylene / 1-butene copolymer, ethylene / 1-hexene copolymer, ethylene / 1-octene copolymer, ethylene-4-methyl-1-pentene copolymer , Ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-acrylic acid ester copolymer, ethylene-based polymer such as ethylene-methacrylic acid ester copolymer, polypropylene , Propylene / ethylene copolymers, propylene polymers such as propylene / 1-butene copolymer, poly 1-butene, poly 1-hexene, poly 4-methyl-1-pentene, and the like. The combination may be used alone or in combination of two or more. Among such olefin polymers, low-density polyethylene, high-density polyethylene, ethylene · 1 because of excellent adhesion to a substrate when subjected to extrusion lamination molding, and excellent film moldability and cost performance. -Butene copolymer, ethylene / 1-hexene copolymer, and ethylene / 1-octene copolymer are particularly preferred.

  Since the olefin polymer used in the (A) layer and the (B) layer of the present invention is excellent in adhesion to a substrate when subjected to film moldability or extrusion laminate molding, JIS K6922-1 (1997). The melt mass flow rate (hereinafter referred to as MFR) is preferably in the range of 0.1 to 100 g / 10 min.

Moreover, the olefin polymer used for the (A) layer and the (B) layer of the present invention has releasability when the density measured in accordance with JIS K6922-1 (1997) is in the range of 880 to 970 kg / m ^3. It is preferable because it is excellent. If the density is too low, the heat resistance of the release film is insufficient in the pressure-sensitive adhesive application step, and the adhesive strength between the pressure-sensitive adhesive and the release film may increase. On the other hand, if the density is too high, the rigidity of the film may become too high.

The titanium oxide used in the layer (A) of the present invention is an oxide of titanium represented by the composition formula TiO ₂ and is mainly used as a white pigment. Moreover, it may mix with another pigment and may be used as a toning agent.

  Such titanium oxide is commercially available from Ishihara Sangyo Co., Ltd. under the trade name “Taipaek” and from Teika Co., Ltd. under the trade name TITANIX. Moreover, such a titanium oxide is marketed by Tokyo Ink Co., Ltd. under the trade name PEX6800 White as a master batch in which high concentration is added to the olefin resin.

  The layer (A) constituting the present invention is formed from a material composed of an olefin polymer containing 0.1 to 20% by weight of titanium oxide. When the titanium oxide is less than 0.1% by weight, the function as a colorant cannot be exhibited, and thus it is not preferable, and when it is 20% by weight or more, the film formability is inferior.

  Moreover, you may add another pigment, antioxidant, a lubricant, a neutralizing agent, an antiblocking agent, surfactant, and a slip agent to the (A) layer which comprises this invention as needed.

  The titanium oxide and the olefin polymer used for the layer (A) of the present invention can be produced by a commonly used resin mixing apparatus. For example, a single-screw extruder, a twin-screw extruder, a Banbury mixer, a pressure kneader, a melt kneader such as a rotating roll, a Henschel mixer, a V blender, a ribbon blender, a tumbler, and the like can be given. When using a melt-kneading apparatus, the melting temperature is preferably about the melting point of the olefin polymer to about 350 ° C.

  The polydimethylsiloxane used in the layer (B) of the present invention is not particularly limited, but preferably has a viscosity at 25 ° C. of 50 cSt or more from the viewpoint of extrusion moldability.

  The polydimethylsiloxane used in the present invention may be one in which some side chains and / or terminal methyl groups are substituted with other functional groups. Such functional groups are not particularly limited, such as vinyl group, hydroxyl group, alkoxy group, amino group, epoxy group, polyether group, aralkyl group, carbinol group, mercapto group, carboxyl group, phenyl group, hydrogen, etc. Can be illustrated. Among such polydimethylsiloxanes, represented by the following structural formula (1), R is an alkyl group having 1 to 30 carbon atoms, a phenyl group, a fluoroalkyl group having 3 to 30 carbon atoms, and 6 or more carbon atoms. One or more functional groups selected from the group consisting of 30 or less fatty acid amide groups, methacrylic groups and epoxy groups are preferred because of their excellent release properties, and among them, methyl groups, phenyl groups and epoxy groups are most preferred.

（式中、ｍは１０以上の整数、ｎは１以上の整数である。ここで官能基Ｒは分子中にランダムに導入されていてもよい。）
炭素数１以上３０以下のアルキル基としてはメチル基、エチル基、プロピル基、ブチル基等、炭素数３以上３０以下のフルオロアルキル基としてはフルオロエチル基、フルオロブチル基等、炭素数６以上３０以下の脂肪酸アミド基としてはステアリン酸アミド基、オレイン酸アミド基、パルミチン酸アミド基、エルカ酸アミド基等が挙げられる。

(In the formula, m is an integer of 10 or more, and n is an integer of 1 or more. Here, the functional group R may be randomly introduced into the molecule.)
Examples of the alkyl group having 1 to 30 carbon atoms include a methyl group, an ethyl group, a propyl group, and a butyl group. Examples of the fluoroalkyl group having 3 to 30 carbon atoms include a fluoroethyl group and a fluorobutyl group. Examples of the fatty acid amide group include a stearic acid amide group, an oleic acid amide group, a palmitic acid amide group, and an erucic acid amide group.

  In addition, when R has a structure containing an epoxy group, it is preferable that the epoxy equivalent of polydimethylsiloxane is 500 g / mol or more and 50000 g / mol or less because of excellent release properties.

  Examples of such polydimethylsiloxane include unmodified polydimethylsiloxane having no functional group other than methyl group (sometimes referred to as straight silicone oil), phenyl group-modified polydimethylsiloxane, methacryl-modified polydimethylsiloxane, Examples include fluoro group-modified polydimethylsiloxane, long-chain alkyl group-modified polydimethylsiloxane, higher fatty acid ester-modified polydimethylsiloxane, fatty acid amide-modified polydimethylsiloxane, and epoxy-modified polydimethylsiloxane. These polydimethylsiloxanes may be used alone or in combination of two or more.

  Examples of such polydimethylsiloxanes include Shin-Etsu Silicone KF-96, KF-50, KF-54, KF-1001, and KF-102 from Shin-Etsu Chemical Co., Ltd., and trade name SH200 from Toray Dow Corning Co., Ltd. Are commercially available.

  When the curing catalyst containing tin and / or titanium in the molecule is used in combination with the olefin polymer and polydimethylsiloxane constituting the layer (B) of the present invention, a two-component comprising the olefin polymer and polydimethylsiloxane. Compared to a system composition, it is preferable because the releasability is improved and the amount of expensive polydimethylsiloxane can be reduced. Although its action has not been clarified, it is considered that it has an effect of reacting and crosslinking the functional group formed on polydimethylsiloxane by the oxidation treatment of the film surface.

  Specific examples of the curing catalyst used in the present invention include dibutyltin dilaurate, dibutyltin dimaleate, dioctyltin dilaurate, organotin compounds such as tin octylate, alkoxytitanium compounds such as tetraisopropoxytitanium and tetrabutoxytitanium, Examples thereof include organic titanium compounds such as titanate compounds such as tetraisopropyl titanate and tetranormal butyl titanate. Of these, butyltin compounds such as dibutyltin dilaurate and dibutyltin dimaleate, and octyltin compounds such as dioctyltin dilaurate and tin octylate are preferred because of their high releasability improving effect. Among them, dioctyltin dilaurate is preferable It is particularly preferable because of its excellent balance with the above.

  The compounding in the resin composition constituting the layer (B) of the present invention is 93 to 99.99% by weight of olefin polymer and 0.01 to 7% by weight of polydimethylsiloxane. Further, a curing catalyst containing tin and / or titanium in the molecule is 0.001 with respect to 100 parts by weight of a composition comprising 93 to 99.99% by weight of an olefin polymer and 0.01 to 7% by weight of polydimethylsiloxane. When it is blended in an amount of ˜1 part by weight, it is preferable because the effect of improving releasability is high. Most preferably, the curing catalyst containing tin and / or titanium in the molecule is 0.01 to 0.5 part by weight.

  When the polydimethylsiloxane is less than 0.01% by weight, the release property of the laminate is inferior, which is not preferable. When it exceeds 7% by weight, the film formability is inferior, which is not preferable. In addition, it is preferable that the resin composition constituting the layer (B) does not contain titanium oxide because it is excellent in releasability.

Moreover, the olefin polymer used for the (B) layer is an additive usually used for an olefin resin, such as an antioxidant, a lubricant, a neutralizer, an antiblocking agent, a surfactant, and a slip agent, as necessary. May be added within a range that does not impair the releasability.
The releasable resin composition used for the layer (B) of the present invention can be produced by a commonly used resin mixing apparatus. For example, a single-screw extruder, a twin-screw extruder, a Banbury mixer, a pressure kneader, a melt kneader such as a rotating roll, a Henschel mixer, a V blender, a ribbon blender, a tumbler, and the like can be given. When using a melt-kneading apparatus, the melting temperature is preferably about the melting point of the olefin polymer to about 350 ° C.

  The (B) layer surface of the laminate of the present invention is preferably oxidized in order to suppress the transfer of the release agent to the adhesive surface of the tape or label. Further, the peeling strength is reduced by the oxidation, and the releasability can be improved.

  (B) Examples of oxidation treatment methods for oxidizing the surface of the layer include chromic acid treatment, sulfuric acid treatment, air oxidation, ozone treatment, corona discharge treatment, flame treatment, plasma treatment, and the like. An oxide is applied to the surface of the polyolefin resin. Corona discharge treatment, flame treatment, and plasma treatment are particularly preferred for effective formation.

Corona discharge treatment is widely used as a continuous treatment technique for plastic film and sheet surfaces, and is performed by passing the film through a corona atmosphere generated by a corona discharge treatment machine. The corona discharge density is preferably 1 to 100 W · min / m ² because of excellent re-tackiness of the pressure-sensitive adhesive.

  The flame treatment is performed by bringing the film surface into contact with a flame generated when natural gas, propane, or the like is burned.

  Plasma treatment is an excited inert gas that is electrically neutral after removing charged particles by electronically exciting a single or mixed gas such as argon, helium, neon, hydrogen, oxygen, and air with a plasma jet. Is sprayed onto the film surface.

  The thicknesses of the (A) layer and the (B) layer constituting the present invention are not particularly limited as long as the object of the present invention is achieved, and is excellent in flexibility and has few problems such as breakage. The thickness is preferably 5 mm, and the range of 1 μm to 100 μm is most preferable from the viewpoint of economy.

  The laminate of the present invention can be produced using a calendar molding machine, a press molding machine, an extrusion laminating machine or the like. In extrusion lamination molding, the coextrusion lamination method and the tandem lamination method are most preferable from the viewpoint of economy.

  When subjected to extrusion laminating, the extrusion resin temperature of the olefin polymer used for the layer (A) and the releasable resin composition used for the layer (B) is preferably in the range of 200 to 350 ° C., more preferably It is the range of 240-340 degreeC. When the extrusion resin temperature of the olefin-based polymer used for the (A) layer and the releasable resin composition used for the (B) layer is less than 200 ° C., in the obtained laminate, the base material / (A) interlayer and The adhesive strength between the (A) layer / (B) layer may be lowered. On the other hand, when the extrusion resin temperature of the olefin polymer used for the (A) layer and the releasable resin composition used for the (B) layer exceeds 350 ° C., the resin deteriorates, and the desired performance cannot be obtained. Sometimes.

  The laminate of the present invention is extremely useful as a wide range of industrial materials such as labels, sealing release papers, and adhesive tape substrates.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples.

  The measurement methods and evaluation methods for physical properties and workability are shown below.

(1) Melt mass flow rate (MFR)
It measured based on JISK6922-1 (1997).

(2) Density The density was measured in accordance with JIS K6922-1 (1997).

(3) Release property A cloth adhesive tape (product name No. 102N, manufactured by Nichiban Co., Ltd.) having a width of 50 mm and a length of 150 mm was applied to the surface of the release film side of the laminate obtained in the example, and a linear pressure of 5 kg / cm. After passing between rubber rolls at a speed of 5 m / min, the sample was allowed to stand in an atmosphere of 40 ° C. for 7 days to obtain a sample for measuring releasability. Thereafter, the peel strength between the craft adhesive tape and the release film was measured with a tensile tester (manufactured by Shimadzu Corporation, trade name: Autograph DCS-100). The peeling speed is 500 mm / min.

(4) Re-adhesive property The cloth adhesive tape having a width of 50 mm peeled from the surface of the release film by the above-described releasability test was applied to an aluminum plate (trade name A1N30H-H18, manufactured by Toyo Aluminum Co., Ltd., thickness 0.1 mm) at 5 kg / Affixed with a linear pressure of cm. After leaving in an atmosphere of 23 ° C. for 1 day, the adhesive strength between the craft adhesive tape and the aluminum plate was measured with a tensile tester (Autograph DCS-100, manufactured by Shimadzu Corporation). The peeling speed is 300 mm / min. When the pressure-sensitive adhesive surface of the pressure-sensitive adhesive tape is contaminated by the release film, the adhesive strength of the pressure-sensitive adhesive tape is lowered and the performance as the pressure-sensitive adhesive tape is impaired. That is, the higher the adhesive strength, the better the re-tackiness.

Example 1
As an olefin polymer, low-density polyethylene (trade name Petrocene 205 manufactured by Tosoh Corp., hereinafter sometimes referred to as LDPE-A) having an MFR of 3 g / 10 min and a density of 924 kg / m ³ is 99% by weight, poly Straight silicone oil (trade name Shin-Etsu Silicone KF-96 manufactured by Shin-Etsu Chemical Co., Ltd., viscosity 10,000 cSt, hereinafter may be referred to as B-1) as dimethylsiloxane is blended so as to be 1% by weight. It was melt-kneaded in an extruder (Toyo Seiki Laboplast Mill) to obtain pellets of a releasable resin composition used for the (B) layer.

On the corona-treated surface of high-quality paper (product name Kinmari SW, basis weight 50 g / m ² manufactured by Hokuetsu Paper Co., Ltd.) subjected to corona treatment under the condition of 50 W · min / m ² as a base material, LDPE− as a layer (A) 90% by weight of A (trade name Petrocene 205 manufactured by Tosoh Corp.), 10% of a master batch of titanium oxide (composed of Tokyo Ink Co., Ltd. product name PEX6800 White, LDPE 40% by weight and titanium oxide 60% by weight) % Pellets were supplied to an extruder of an extrusion laminator having a 90 mmφ screw, extruded from a T-die at a temperature of 320 ° C., and laminated to a thickness of 15 μm.

Further, on the surface of the layer (A), as the layer (B), the releasable resin composition obtained by the above method is supplied to an extruder of an extrusion laminator having a 90 mmφ screw, and the T die is used at a temperature of 320 ° C. After extruding and laminating to a thickness of 20 μm, the surface of layer (B) was subjected to corona treatment under the condition of 15 W · min / m ² to obtain a laminate.

  After the obtained laminate was stored in an oven kept at 40 ° C. for 20 hours, the releasability, re-tackiness, and adhesion to the substrate were measured, and the measurement results are shown in Table 1.

実施例２
（Ｂ）層として、ＬＤＰＥ−Ａを９９重量％、ポリジメチルシロキサン（Ｂ−１）を１重量％の代わりに、ＬＤＰＥ−Ａを９９．５重量％、ポリジメチルシロキサン（Ｂ−１）を０．５重量％とした以外は、実施例１と同様にして積層体を得た。評価結果は表１に示した。

Example 2
As the layer (B), instead of 99% by weight of LDPE-A and 1% by weight of polydimethylsiloxane (B-1), 99.5% by weight of LDPE-A and 0% of polydimethylsiloxane (B-1) were used. A laminate was obtained in the same manner as in Example 1 except that the content was changed to 5% by weight. The evaluation results are shown in Table 1.

Example 3
As the layer (B), 99% by weight of LDPE-A, 1% by weight of polydimethylsiloxane (B-1), 99% by weight of LDPE-A, polydimethylsiloxane, epoxy equivalent of 3500 g / mol, viscosity Example 1 except that the epoxy-modified polydimethylsiloxane of 17000 cSt (trade name Shin-Etsu Silicone KF-1001, manufactured by Shin-Etsu Chemical Co., Ltd., hereinafter sometimes referred to as B-2) was 1% by weight. To obtain a laminate. The evaluation results are shown in Table 1.

Example 4
As the layer (B), instead of 99% by weight of LDPE-A and 1% by weight of polydimethylsiloxane (B-1), 99% by weight of LDPE-A and 0.5% of polydimethylsiloxane (B-2) were used. A laminate was obtained in the same manner as in Example 1 except that the amount was changed to% by weight. The evaluation results are shown in Table 1.

Example 5
As the layer (B), instead of 99% by weight of LDPE-A and 1% by weight of polydimethylsiloxane (B-1), 98.5% by weight of LDPE-A and 1 of polydimethylsiloxane (B-2) A laminate was obtained in the same manner as in Example 1 except that the content was changed to 5% by weight. The evaluation results are shown in Table 1.

Example 6
As the layer (B), instead of 99% by weight of LDPE-A and 1% by weight of polydimethylsiloxane (B-1), 99% by weight of LDPE-A and polydimethylsiloxane were used as methylphenyl silicone oil (Shin-Etsu Chemical). A laminate was obtained in the same manner as in Example 1 except that the product name Shin-Etsu Silicone KF-50, viscosity 3,000 cSt, hereinafter may be referred to as B-3) manufactured by Kogyo Co., Ltd. was 1% by weight. . The evaluation results are shown in Table 2.

実施例７
（Ｂ）層として、ＬＤＰＥ−Ａを９９重量％、ポリジメチルシロキサン（Ｂ−１）を１重量％の代わりに、ＬＤＰＥ−Ａを９８．９８重量％、ポリジメチルシロキサン（Ｂ−１）を１重量％、硬化触媒としてジラウリン酸ジオクチル錫を０．０２重量％とした以外は、実施例１と同様にして積層体を得た。評価結果は表２に示した。

Example 7
As the layer (B), instead of 99% by weight of LDPE-A and 1% by weight of polydimethylsiloxane (B-1), 98.98% by weight of LDPE-A and 1 of polydimethylsiloxane (B-1) are used. A laminate was obtained in the same manner as in Example 1 except that 0.02% by weight of dioctyltin dilaurate was used as a curing catalyst. The evaluation results are shown in Table 2.

Example 8
As the layer (B), instead of 99% by weight of LDPE-A and 1% by weight of polydimethylsiloxane (B-1), MFR is 7.5 g / 10 min and density is 902 kg / m as an olefin polymer. ³ except that the ethylene / 1-octene copolymer (trade name Affinity PT1450 manufactured by Dow Chemical Co., Ltd., sometimes referred to as LLDPE) is 99% by weight and polydimethylsiloxane (B-1) is 1% by weight. A laminate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 2.

Example 9
(A) As a layer, LDPE-A 90% by weight, titanium oxide masterbatch 10% by weight, LDPE-A 45% by weight, high-density polyethylene (trade name Nipolon Hard 2000, MFR 15 g, manufactured by Tosoh Corporation) / 10 min, density 960 kg / m ³ , hereinafter sometimes referred to as HDPE), and 45 wt%, titanium oxide masterbatch was 10 wt%, and a laminate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 2.

Comparative Example 1
(A) As a layer, LDPE-A 90 wt%, titanium oxide masterbatch instead of 10 wt%, LDPE-A 100 wt%, and (B) layer LDPE-A 99 wt%, Instead of 1% by weight of dimethylsiloxane (B-1), LDPE-A was 89% by weight, polydimethylsiloxane (B-1) was 1% by weight, and the master batch of titanium oxide was 10% by weight. A laminate was obtained in the same manner as in Example 1. The evaluation results are shown in Table 3. The peel strength was high and the mold release property was poor.

比較例２
ＬＤＰＥ−Ａを８９．５重量％、ポリジメチルシロキサン（Ｂ−１）を０．５重量％、酸化チタンのマスターバッチを１０重量％とした以外は、比較例１と同様にして積層体を得た。評価結果を表３に示すが、剥離強度が高く離型性に劣っていた。

Comparative Example 2
A laminate was obtained in the same manner as in Comparative Example 1 except that 89.5% by weight of LDPE-A, 0.5% by weight of polydimethylsiloxane (B-1), and 10% by weight of the master batch of titanium oxide were used. It was. The evaluation results are shown in Table 3. The peel strength was high and the mold release property was poor.

Comparative Example 3
The layer (B) was laminated in the same manner as in Example 1, except that 99% by weight of LDPE-A and 1% by weight of polydimethylsiloxane (B-1) were replaced by 100% by weight of LDPE-A. Got the body. The evaluation results are shown in Table 3, but the peel strength was too high to measure the peel strength, and the release properties were inferior.

Comparative Example 4
As the layer (B), LDPE-A is 99% by weight, polydimethylsiloxane (B-1) is 1% by weight, LDPE-A is 92% by weight, and polydimethylsiloxane (B-1) is 8% by weight. A laminate was produced in the same manner as in Example 1, except that the laminate could not be obtained due to poor extrusion.

Comparative Example 5
As the layer (B), 89% by weight of LDPE-A, 1% by weight of polydimethylsiloxane (B-1), 10% by weight of the master batch of titanium oxide, 89% by weight of LDPE-A, polydimethyl A laminate was obtained in the same manner as in Comparative Example 1 except that 1% by weight of siloxane (B-2) and 10% by weight of the master batch of titanium oxide were used. The evaluation results are shown in Table 3. The peel strength was high and the mold release property was poor.

Claims (6)

A laminate comprising: (A) a layer satisfying the following requirements on at least one surface of a substrate; and (B) a layer satisfying the following requirements on the (A) layer.
(A) Layer: A layer made of an olefin polymer containing 0.1 to 20% by weight of titanium oxide.
(B) Layer: A layer composed of a releasable resin composition composed of 93 to 99.99% by weight of an olefin polymer and 0.01 to 7% by weight of polydimethylsiloxane. The release resin composition used for the layer (B) is in a molecule with respect to 100 parts by weight of a composition comprising 93 to 99.99% by weight of an olefin polymer and 0.01 to 7% by weight of polydimethylsiloxane. The laminate according to claim 1, wherein 0.001 to 1 part by weight of a curing catalyst containing tin and / or titanium is blended. The laminate according to claim 1 or 2, wherein the polydimethylsiloxane is represented by the following structural formula, and R is either a methyl group or a phenyl group.

(In the formula, m is an integer of 10 or more, and n is an integer of 1 or more.) The laminate according to claim 1 or 2, wherein the polydimethylsiloxane is a polydimethylsiloxane having an epoxy group having a functional group equivalent of 500 g / mol or more and 50000 g / mol or less. The layered product according to any one of claims 1 to 4, wherein the layer surface is oxidized by at least one treatment method selected from corona discharge treatment, flame treatment or plasma treatment. The laminate according to any one of claims 1 to 5, wherein the substrate is at least one selected from paper, a woven fabric or a nonwoven fabric made of natural material or synthetic resin.