WO2012105339A1

WO2012105339A1 - Release agent, manufacturing method therefor, release material, and pressure-sensitive adhesive tape

Info

Publication number: WO2012105339A1
Application number: PCT/JP2012/051214
Authority: WO
Inventors: 悠司豊田; 平松　剛
Original assignee: 日東電工株式会社
Priority date: 2011-02-04
Filing date: 2012-01-20
Publication date: 2012-08-09
Also published as: JP2012162623A

Abstract

The present invention provides a method for manufacturing a release agent that contains a non-reactive polyolefin (A), an isocyanate (B), and a polyolefin polyol (C). Said non-reactive polyolefin (A) contains: an ethylene α-olefin copolymer (A-1) that has a specific Young's modulus and tensile failure stress; and a propylene α-olefin copolymer (A-2). The amount of the ethylene α-olefin copolymer (A-1) used is at least 90% of the weight of the non-reactive polyolefin (A), and the amount of the propylene α-olefin copolymer (A-2) used is at least 0.1% but less than 10% of the weight of the non-reactive polyolefin (A).

Description

Release agent, method for producing the same, release material, and adhesive tape

The present invention relates to a release agent, a production method thereof, a release material, and an adhesive tape.

The release material is provided with a release agent layer on at least one surface of a substrate such as paper, plastic film and plastic laminated paper, and is intended to protect the adhesive surface of an adhesive tape, an adhesive sheet, a label, etc. It is used in manufacturing processes for green sheets.

As a release agent for forming a release agent layer, a silicone release agent, a long-chain alkyl release agent, a polyolefin release agent, a fluorine release agent, and the like are known. However, in applications related to electronic parts and the like, there are cases in which silicone-based release agents cause problems, and therefore non-silicone release agents such as polyolefin-based release agents are used.

As polyolefin release agents, those containing an isocyanate cross-linking agent and a polyol in addition to polyolefin are known in order to improve substrate adhesion (for example, Patent Documents 1 to 3).

JP 2004-346213 A Japanese Patent Laid-Open No. 2004-250681 JP 2004-230773 A

There are various uses of the release agent layer formed from the release agent. Depending on the application, the release agent layer is required to have a low peel strength or, conversely, a high peel force to some extent. In order to adjust the peeling force by changing the type of the release agent component in accordance with such various uses, it is necessary to study for changing the component, change the factory equipment, and the like, which is very troublesome.

The present invention has been made paying attention to the above circumstances, and an object of the present invention is to provide a method for producing a release agent that can easily adjust the release force of the release agent.

As a result of intensive studies by the present inventors, if an olefin-based release agent mainly containing an ethylene-based α-olefin copolymer (A-1) having a low tensile modulus and tensile fracture stress is used, the release force It has been found that a release agent layer having a small thickness can be formed. Further, by adding the propylene-based α-olefin copolymer (A-2) to the olefin-based release agent, the release force can be increased according to the amount of the propylene-based α-olefin copolymer (A-2) added. It was found that it can be easily adjusted. The present invention based on these findings is as follows.

[1] A method for producing a release agent containing non-reactive polyolefin (A), isocyanate (B) and polyolefin polyol (C),
The amount of non-reactive polyolefin (A) used is 80 parts by weight or more in 100 parts by weight of the obtained release agent,
The non-reactive polyolefin (A) includes an ethylene-based α-olefin copolymer (A-1) in which the amount of ethylene constitutional units in the copolymer is 50 mol% or more, and the amount of propylene constitutional units in the copolymer. Containing a propylene-based α-olefin copolymer (A-2) of more than 50 mol%,
The ethylene-based α-olefin copolymer (A-1) has a tensile modulus at 23 ° C. of 10 MPa or less, and a tensile fracture stress at 23 ° C. of 8 MPa or less.
The amount of the ethylene-based α-olefin copolymer (A-1) used is 90 parts by weight or more in 100 parts by weight of the non-reactive polyolefin (A),
A method wherein the amount of the propylene-based α-olefin copolymer (A-2) used is 0.1 to 10 parts by weight per 100 parts by weight of the non-reactive polyolefin (A).
[2] The method according to [1] above, wherein the isocyanate (B) is a polyisocyanate having 3 or more isocyanate groups in one molecule.
[3] The method according to [2] above, wherein the polyisocyanate is at least one selected from the group consisting of an aromatic polyisocyanate and an alicyclic polyisocyanate.
[4] The method according to [3], wherein the polyisocyanate is at least one selected from the group consisting of a polyhydric alcohol adduct of an aromatic diisocyanate and a polyhydric alcohol adduct of an alicyclic diisocyanate.
[5] The amount of the isocyanate (B) used is any one of the above [1] to [4], which is 0.5 to 20 parts by weight with respect to 100 parts by weight of the non-reactive polyolefin (A). the method of.
[6] The method according to any one of [1] to [5] above, wherein the number average molecular weight of the polyolefin polyol (C) is 1500 to 50000.
[7] A release agent produced by the method according to any one of [1] to [6] above.
[8] A release material having a substrate and a release agent layer,
A release material having a release agent layer formed from the release agent according to the above [7] on at least one side of the substrate.
[9] An adhesive tape having an adhesive layer and the release material according to [8] above,
An adhesive tape in which the adhesive layer and the release agent layer of the release material are in contact.
[10] A pressure-sensitive adhesive tape having a base material, a pressure-sensitive adhesive layer and a release agent layer,
Having a release agent layer formed from the release agent according to [7] above on one side of the substrate,
A pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer on the other surface of a substrate on which a release agent layer is not formed.

According to the method for producing a release agent of the present invention, the release force of the release agent can be easily adjusted without changing the type of the release agent component.

1. TECHNICAL FIELD The present invention provides a method for producing a release agent containing non-reactive polyolefin (A), isocyanate (B) and polyolefin polyol (C), and a release agent produced by this method. Hereinafter, the release agent component will be described in order.

[Non-reactive polyolefin (A)]
In the present invention, “non-reactive polyolefin (A)” means a polyolefin that does not react with isocyanate (B) and polyolefin polyol (C) described later. Non-reactive polyolefin (A) does not contain, for example, a functional group that reacts with isocyanate (B) and polyolefin polyol (C), such as a hydroxyl group (hydroxy group), an amino group, a carboxy group, an isocyanate group (isocyanato group), and the like. Polyolefin. In the present invention, “polyolefin” means homopolymers and copolymers containing only olefin structural units.

The content of the non-reactive polyolefin (A) is 80 parts by weight or more, preferably 85 parts by weight or more, more preferably 90 parts by weight or more in 100 parts by weight of the release agent. When content of non-reactive polyolefin (A) is less than 80 weight part, there exists a tendency for the peeling force of the obtained release agent layer to become large. In addition, there is no limitation in particular in the upper limit of content of non-reactive polyolefin (A). However, in order to ensure a sufficient amount of isocyanate (B) and polyolefin polyol (C) to obtain sufficient release agent layer strength, the content of the non-reactive polyolefin (A) is preferably 99 in the release agent. The amount is not more than parts by weight, more preferably not more than 98 parts by weight. In addition, the amount of the organic solvent is not included in “100 parts by weight of the release agent” and “release agent” which are the reference for the content.

The non-reactive polyolefin (A) includes one or more ethylene-based α-olefin copolymers (A-1) and one or more propylene-based α-olefin copolymers (A-2). Containing. The α-olefin copolymer may be any of a random copolymer, a block copolymer, and a graft copolymer. In the present invention, the ethylene-based α-olefin copolymer means an α-olefin copolymer in which the amount of ethylene structural units in the copolymer is 50 mol% or more, and the propylene-based α-olefin in the copolymer. The copolymer means an α-olefin copolymer having a propylene structural unit amount exceeding 50 mol%. Further, the tensile modulus at 23 ° C. of the ethylene-based α-olefin copolymer (A-1) is 10 MPa or less, and the tensile fracture stress at 23 ° C. is 8 MPa or less.

The ethylene structural unit amount in the ethylene-based α-olefin copolymer (A-1) is 50 mol% or more, preferably 60 to 95 mol%, more preferably 70 to 95 mol%. The α-olefin structural unit of the ethylene-based α-olefin copolymer (A-1) is preferably at least one monomer selected from the group consisting of propylene and an α-olefin having 4 to 20 carbon atoms, more preferably Is formed from at least one monomer selected from the group consisting of propylene, 1-butene, 1-hexene and 1-octene. Examples of the α-olefin having 4 to 20 carbon atoms include 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl-1-pentene. 1-heptene, 1-octene, 1-decene, 1-dodecene and the like.

The ethylene-based α-olefin copolymer (A-1) is more preferably at least one selected from the group consisting of an ethylene-propylene copolymer and an ethylene-1-butene copolymer. Such an ethylene-1-butene copolymer may contain a structural unit derived from an α-olefin other than ethylene and 1-butene in an amount of 10 mol% or less. Similarly, the ethylene-propylene copolymer may contain a structural unit derived from an α-olefin other than ethylene and propylene in an amount of 10 mol% or less. The ethylene-based α-olefin copolymer (A-1) is obtained by, for example, using a catalyst comprising a transition metal catalyst component (for example, a vanadium compound or a zirconium compound) and an organoaluminum compound catalyst component to produce ethylene and α-olefin. It can be produced by copolymerization.

The amount of the propylene structural unit in the propylene-based α-olefin copolymer (A-2) is more than 50 mol%, preferably 60 to 95 mol%, more preferably 70 to 95 mol%. The α-olefin structural unit contained in the propylene-based α-olefin copolymer (A-2) is preferably at least one monomer selected from the group consisting of ethylene and an α-olefin having 4 to 20 carbon atoms. And more preferably at least one monomer selected from the group consisting of ethylene, 1-butene, 1-hexene and 1-octene. Examples of the α-olefin having 4 to 20 carbon atoms include those described above.

The propylene-based α-olefin copolymer (A-2) is more preferably a propylene-ethylene random copolymer (propylene-based elastomer). This propylene-ethylene random copolymer may contain a constituent unit derived from α-olefin other than propylene and ethylene in an amount of 10 mol% or less. The propylene-based α-olefin copolymer (A-2) can be produced using a metallocene-based catalyst as described in, for example, JP-A-2000-191862.

The non-reactive polyolefin (A) is a polyolefin other than the ethylene-based α-olefin copolymer (A-1) and the propylene-based α-olefin copolymer (A-2) (hereinafter referred to as “polyolefin (A-3)”). Abbreviated)). Polyolefin (A-3) may be used alone or in combination of two or more. However, the non-reactive polyolefin (A) is preferably composed of an ethylene-based α-olefin copolymer (A-1) and a propylene-based α-olefin copolymer (A-2).

As polyolefin (A-3),
(I) an ethylene-based α-olefin copolymer in which the tensile modulus at 23 ° C. and / or the tensile fracture stress at 23 ° C. does not satisfy the above requirements for the ethylene-based α-olefin copolymer (A-1) (hereinafter “ (Hereinafter abbreviated as “ethylene-based α-olefin copolymer (A-4)”), and (ii) both the ethylene constituent unit amount and the propylene constituent unit amount in the copolymer are ethylene-based α-olefin copolymers. And a polyolefin that does not satisfy the above requirements for a propylene-based α-olefin copolymer (hereinafter abbreviated as “polyolefin (A-5)”).
There is.

As the ethylene-based α-olefin copolymer (A-4), (i) an ethylene-based α-olefin copolymer having a tensile fracture stress at 23 ° C. of 8 MPa or less and a tensile elastic modulus at 23 ° C. exceeding 10 MPa; (Ii) an ethylene-based α-olefin copolymer having a tensile modulus at 23 ° C. of 10 MPa or less and a tensile fracture stress at 23 ° C. exceeding 8 MPa; and (iii) a tensile modulus at 23 ° C. exceeding 10 MPa; An ethylene-based α-olefin copolymer having a tensile fracture stress at 8 ° C. exceeding 8 MPa. Of these, the ethylene-based α-olefin copolymer (A-4) of the embodiment (ii) is preferable.

Polymethylpentene can also be used as the polyolefin (A-5). Examples of polymethylpentene include a homopolymer of 4-methyl-1-pentene, and a copolymer of 4-methyl-1-pentene and other α-olefins. The amount of 4-methyl-1-pentene constituent unit in the polymethylpentene copolymer is preferably 50 to 95 mol%, more preferably 70 to 95 mol%. The polymethylpentene may be a crystalline polymer. The density of polymethylpentene is preferably 0.83 to 0.86 g / cm ³ . Examples of the α-olefin structural unit in the polymethylpentene copolymer include 2 carbon atoms such as ethylene, propylene, 1-butene, 1-hexene, 1-octene, 1-decene, 1-tetradecene, 1-octadecene and the like. Those derived from .alpha.-olefins of .about.20 are preferred. Of these, 1-decene, 1-tetradecene and 1-octadecene, which exhibit good copolymerizability with 4-methyl-1-pentene, are more preferred. An example of a commercially available product of polymethylpentene is TPX-S (4-methylpentene-1-α-olefin copolymer, manufactured by Mitsui Chemicals).

Diene rubbers such as polyisoprene and polybutadiene can also be used as the polyolefin (A-5) as long as they are dissolved in an organic solvent. Such polyisoprene has a cis-1,4 bond of 90% or more, a density of 0.90 to 0.92 g / cm ³ , and a Mooney viscosity (ML1 + 4 at 100 ° C.) of 40 to 70. Those are preferred. Examples of commercially available products of polyisoprene include IR-307 and IR-310 (manufactured by Kraton Polymer Co., Ltd.). As the polybutadiene, those having a cis-1,4 bond of 90% or more, a density of 0.88 to 0.91 g / cm ³ , and a Mooney viscosity (ML1 + 4 at 100 ° C.) of 25 to 50 are preferable. Examples of commercially available products of polybutadiene include Nipol BR1220, Nipol BR1220L (manufactured by Nippon Zeon), and BR01 (manufactured by JSR).

The tensile modulus at 23 ° C. of the ethylene-based α-olefin copolymer (A-1) is 10 MPa or less, preferably 8 MPa or less, more preferably 7 MPa or less, and even more preferably 6 MPa or less. The tensile fracture stress at 23 ° C. of the polymer (A-1) is 8 MPa or less, preferably 6 MPa or less, more preferably 4 MPa or less. Polyolefins having a tensile modulus of elasticity exceeding 10 MPa at 23 ° C. tend to increase the peeling force of the release agent layer when peeled at a low speed and a high speed, and polyolefins having a tensile breaking stress at 23 ° C. exceeding 8 MPa are peeled at a high speed. There is a tendency to increase the peeling force of the release agent layer when it is applied.

In the present invention, neither the tensile modulus of elasticity at 23 ° C. nor the lower limit of the tensile fracture stress at 23 ° C. of the ethylene-based α-olefin copolymer (A-1) is limited. However, in order to obtain sufficient release agent layer strength (coating film strength), the tensile modulus at 23 ° C. of the ethylene-based α-olefin copolymer (A-1) is preferably 2 MPa or more, more preferably 3 MPa or more. The tensile fracture stress at 23 ° C. is preferably 1 MPa or more, more preferably 2 MPa or more.

The tensile modulus at 23 ° C. of the propylene-based α-olefin copolymer (A-2) and the polyolefin (A-3) is preferably 100 MPa or less, and the tensile fracture stress at 23 ° C. is any Is preferably 35 MPa or less. Further, the tensile modulus at 23 ° C. of the propylene-based α-olefin copolymer (A-2) is preferably more than 10 MPa, and the tensile fracture stress at 23 ° C. is preferably more than 8 MPa.

“Tensile elastic modulus at 23 ° C.” and “tensile fracture stress at 23 ° C.” of non-reactive polyolefin (A) such as ethylene-based α-olefin copolymer (A-1) are values measured by the following methods. It is.
Non-reactive polyolefin (A) was dissolved in toluene to give a 5 to 10% by weight solution, and this was applied onto a release film made of polyethylene terephthalate (PET) using a baker type applicator or a doctor blade type applicator. Then, heat-dry with a hot air dryer (100 ° C., 3 minutes), and immediately after heating and drying in an atmosphere of 23 ° C., a non-reactive polyolefin (A) film having a thickness of 20 μm after drying is produced. To do. If the solubility in toluene is poor, it may be dissolved by heating as necessary. The obtained non-reactive polyolefin (A) film was cut into a strip of 30 mm length x 100 mm width, and the non-reactive polyolefin (A) film was peeled off from the release film, with one short side of the cut film as the axis. Then, the sample is wound tightly in the longitudinal direction to obtain a rod-shaped sample having a length of 30 mm.
This rod-shaped sample was subjected to a tensile test with a tensile tester (manufactured by Shimadzu Corp., Autograph AG-IS type) in a 23 ° C atmosphere under conditions of a distance between chucks of 10 mm and a tensile speed of 50 mm / min. Obtain the stress-strain curve. The tensile modulus is calculated from the slope of the stress-strain curve immediately after the start of tension. Further, the stress when the rod-shaped sample is broken is determined as the tensile fracture stress.

The amount of the ethylene-based α-olefin copolymer (A-1) used (that is, the content in the release agent) is 90 parts by weight or more, preferably 91 parts by weight in 100 parts by weight of the non-reactive polyolefin (A). More preferably, it is 92 parts by weight or more. When the amount of the ethylene-based α-olefin copolymer (A-1) used is less than 90 parts by weight, the propylene-based α-olefin copolymer (A-2) (and the polyolefin (A- Due to the influence of 3)), the peeling force of the release agent layer when peeling at low speed and / or high speed is increased. The upper limit of the amount of ethylene-based α-olefin copolymer (A-1) used is determined by the amount of propylene-based α-olefin copolymer (A-2) and the amount of polyolefin (A-3) used as required. The amount used is usually 99.9 parts by weight or less, preferably 99 parts by weight or less, more preferably 98 parts by weight or less.

By adjusting the amount of the propylene-based α-olefin copolymer (A-2) used, the release force of the obtained release agent can be adjusted. However, if the propylene-based α-olefin copolymer (A-2) is used excessively, the peeling force becomes too large. Therefore, the amount of the propylene-based α-olefin copolymer (A-2) used (ie, the content in the release agent) must be suppressed to less than 10 parts by weight in 100 parts by weight of the non-reactive polyolefin (A). is there. The amount of the propylene-based α-olefin copolymer (A-2) used is preferably 9 parts by weight or less, more preferably 8 parts by weight or less in 100 parts by weight of the non-reactive polyolefin (A).

The lower limit of the amount of the propylene-based α-olefin copolymer (A-2) may be appropriately set according to the required peeling force. The amount of the propylene-based α-olefin copolymer (A-2) used is usually 0.1 parts by weight or more, preferably 1 part by weight or more, more preferably 2 parts by weight per 100 parts by weight of the non-reactive polyolefin (A). More than a part.

When polyolefin (A-3) is used, the amount used (that is, the content in the release agent) is selected from ethylene-based α-olefin copolymer (A-1) and propylene-based α-olefin copolymer (A -2) is determined by the amount used. That is, the amount of polyolefin (A-3) used is from non-reactive polyolefin (A) to ethylene α-olefin copolymer (A-1) and propylene α-olefin copolymer (A-2). The remainder after subtracting the amount.

From the viewpoint of solubility in an organic solvent, the density of the non-reactive polyolefin (A) is preferably 0.885 g / cm ³ or less, more preferably 0.880 g / cm ³ or less. When this density exceeds 0.885 g / cm ³ , solubility in an organic solvent tends to be lowered, and application to a substrate tends to be difficult, and peeling force tends to increase. On the other hand, the lower limit of the density of the non-reactive polyolefin (A) is not particularly limited, but this density is preferably 0.830 g / cm ³ or more, more preferably 0.857 g / cm ³ or more, and still more preferably 0.8. It is 858 g / cm ³ or more. The density of the ethylene-based α-olefin copolymer (A-1) is preferably 0.857 g / cm ³ or more and 0.885 g / cm ³ or less (more preferably 0.880 g / cm ³ or less). The density of the propylene-based α-olefin copolymer (A-2) is preferably 0.858 g / cm ³ or more and 0.885 g / cm ³ or less (more preferably 0.880 g / cm ³ or less).

MFR (melt) of ethylene-based α-olefin copolymer (A-1), propylene-based α-olefin copolymer (A-2) and polyolefin (A-3) at 230 ° C. The flow rate is preferably 100 g / 10 min or less, more preferably 70 g / 10 min or less, still more preferably 50 g / 10 min or less, and particularly preferably 10 g / 10 min or less. Total amount of the ethylene-based α-olefin copolymer (A-1), propylene-based α-olefin copolymer (A-2) and polyolefin (A-3) having such preferable MFR (ie, release agent) The total content is preferably 10 parts by weight or more, more preferably 50 parts by weight or more, in 100 parts by weight of the non-reactive polyolefin (A).

Commercial products can be used as the non-reactive polyolefin (A). For example, commercially available ethylene-based α-olefin copolymers (A-1) include Tuffmer P-0080K, Tuffmer P-0280, Tuffmer A-3570S, Tuffmer P-0680, Tuffmer P-0180, Tuffmer P-0480, Tuffmer P-0275, Tuffmer P-0775 (both manufactured by Mitsui Chemicals) and the like can be mentioned. Examples of commercially available propylene-based α-olefin copolymers (A-2) include the Tuffmer XM series (manufactured by Mitsui Chemicals).

[Isocyanate (B)]
The release agent of the present invention contains one or more isocyanates (B). Isocyanate (B) may be either an aromatic isocyanate or an aliphatic isocyanate. The aliphatic isocyanate may be either a chain aliphatic isocyanate or an alicyclic isocyanate. Among these, aromatic isocyanate and alicyclic isocyanate are preferable. Since aromatic isocyanate and alicyclic isocyanate have low compatibility with the non-reactive polyolefin (A), even if they are used, the peelability of the release agent layer is not impaired. On the other hand, the aromatic isocyanate and alicyclic isocyanate which are incompatible with the non-reactive polyolefin (A) are unevenly distributed between the formed release agent layer and the substrate, and greatly contribute to the improvement of the adhesion.

In order to form a release agent layer excellent in substrate adhesion and heat resistance, the isocyanate (B) is preferably a polyisocyanate having 3 or more isocyanate groups in one molecule, more preferably an aromatic poly. It is at least one selected from the group consisting of isocyanate and alicyclic polyisocyanate, and more preferably at least one selected from the group consisting of polyhydric alcohol adducts of aromatic diisocyanates and polyhydric alcohol adducts of alicyclic diisocyanates. One.

Examples of the aromatic diisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthylene diisocyanate, tolidine diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, and the like. Of these, tolylene diisocyanate and xylylene diisocyanate are preferred.

Examples of the alicyclic diisocyanate include isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, dimer acid diisocyanate, norbornene diisocyanate, trans-cyclohexane diisocyanate, hydrogenated tolylene diisocyanate, and the like. Of these, isophorone diisocyanate and hydrogenated xylylene diisocyanate are preferred.

Examples of the polyhydric alcohol include aliphatic polyhydric alcohols such as ethylene glycol, glycerin, trimethylolpropane, pentaerythritol, ditrimethylolpropane, and dipentaerythritol. Of these, trimethylolpropane is preferred.

Examples of the polyisocyanate include compounds having an isocyanate group at the terminal, obtained by reacting the polyhydric alcohol with an excess amount of the aromatic diisocyanate or the alicyclic diisocyanate. In addition, aromatic diisocyanates or alicyclic diisocyanates (eg, isocyanurates) are also suitable as polyisocyanates. The polyhydric alcohol adduct of aromatic diisocyanate is preferably a polyhydric alcohol adduct of tolylene diisocyanate or xylylene diisocyanate, more preferably a polyhydric alcohol adduct of tolylene diisocyanate. The polyhydric alcohol adduct of tolylene diisocyanate is excellent in reactivity and can achieve excellent substrate adhesion. The polyhydric alcohol adduct of alicyclic diisocyanate is preferably a polyhydric alcohol adduct of hydrogenated xylylene diisocyanate or isophorone diisocyanate.

The amount of the isocyanate (B) used (that is, the content in the release agent) is preferably 0.5 to 20 parts by weight, more preferably 1.50 parts by weight with respect to 100 parts by weight of the non-reactive polyolefin (A). The amount is 0 to 15 parts by weight, more preferably 1.5 to 10 parts by weight. With such a usage amount, there is no adverse effect such as shortening of the pot life of the release agent, and better substrate adhesion can be obtained.

[Polyolefin polyol (C)]
The release agent of the present invention contains one or more polyolefin polyols (C). The polyolefin polyol (C) is used for reacting with the isocyanate (B) in the formation of the release agent layer. As the polyolefin polyol (C), those having good compatibility with the non-reactive polyolefin (A) are preferable.

The number average molecular weight (Mn) of the polyolefin polyol (C) is preferably 1500 to 50000, more preferably 1500 to 4000, and still more preferably 1500 to 3000. The polyolefin polyol (C) having Mn in such a range has moderate solubility in both the non-reactive polyolefin (A) and the isocyanate (B). Therefore, such a polyolefin polyol (C) can improve the release agent layer strength and heat resistance, while maintaining the appearance of the release agent layer. In addition, when this Mn is outside the above range, a release agent layer having a whitish and cloudy appearance may be obtained. Furthermore, if this Mn is within the above range, the hydroxyl group resulting from the polyolefin polyol (C) is not excessive in the release agent layer portion where the isocyanate (B) on the side opposite to the substrate is not unevenly distributed, and the release force Is obtained. Furthermore, if this Mn is within the above range, the isocyanate (B) and the polyolefin polyol (C) can react appropriately in the release agent layer portion where the isocyanate (B) on the substrate side is unevenly distributed, and it is more excellent. The substrate adhesion can be obtained.

In the present invention, the type of polyolefin polyol (C) is not particularly limited. Examples of the polyolefin polyol (C) include polyethylene polyol, polypropylene polyol, polybutadiene polyol, hydrogenated polybutadiene polyol, polyisoprene polyol, and hydrogenated polyisoprene polyol. Among these, hydrogenated polyisoprene polyol and polyisoprene polyol are preferable from the viewpoint of compatibility with the non-reactive polyolefin (A) and influence on peeling force.

Further, the hydroxyl value (mgKOH / g) of the polyolefin polyol (C) is preferably 20 or more from the viewpoint of the release agent layer strength and curability, and is preferably 75 or less from the viewpoint of the influence on the peeling force. A more preferred hydroxyl value (mgKOH / g) is 25-60.

In the present invention, commercially available polyolefin polyol (C) can be used. Examples of such commercially available products include Poly bdR-45HT (hydroxyl-terminated liquid polybutadiene: Mn = 2800, hydroxyl value = 46.6 mgKOH / g, manufactured by Idemitsu Kosan Co., Ltd.), Poly ip (hydroxyl-terminated liquid polyisoprene: Mn = 2500, hydroxyl value = 46.6 mg KOH / g, manufactured by Idemitsu Kosan Co., Ltd.), Epol (hydroxyl-terminated liquid hydrogenated polyisoprene: Mn = 2500, hydroxyl value = 50.5 mg KOH / g, manufactured by Idemitsu Kosan Co., Ltd.), GI-1000 ( Hydroxyl group-containing liquid hydrogenated polybutadiene: Mn = 1500, hydroxyl value = 60 to 75 mgKOH / g, manufactured by Nippon Soda Co., Ltd., GI-2000 (hydroxyl group-containing liquid hydrogenated polybutadiene: Mn = 2100, hydroxyl value = 40 to 55 mgKOH / g, Nippon Soda Co., Ltd.), GI-3000 (Hydroxyl-containing liquid hydrogenated polybutadiene: n = 3000, hydroxyl value = 25 ~ 35mgKOH / g, manufactured by Nippon Soda Co., Ltd.) and the like. These polyolefin polyols (C) are all liquid at room temperature. Unistor P-801 (16% by weight toluene solution of hydroxyl group-containing polyolefin, toluene removed product is solid, hydroxyl value 40 mg KOH / g, manufactured by Mitsui Chemicals, Inc.) can also be used.

The amount of the polyolefin polyol (C) used (that is, the content in the release agent) is represented by the following formula (I):
A = hydroxyl value (mgKOH / g) of polyolefin polyol (C) x number of parts by weight of polyolefin polyol (C) with respect to 100 parts by weight of non-reactive polyolefin (A) (I)
The value of A is preferably set to 30 to 250, more preferably 40 to 200, and still more preferably 50 to 150. If the value of A is less than 30, the release agent layer strength tends to be insufficient, and if it is greater than 250, the release force of the release agent layer tends to be too high.

[Optional ingredients]
The release agent of the present invention may contain one or more optional components. Optional components include, for example, resins other than non-reactive polyolefin (A), antioxidants, ultraviolet absorbers, light stabilizers such as hindered amine light stabilizers and antistatic agents, carbon black, calcium oxide, magnesium oxide, silica And fillers such as zinc oxide and titanium oxide, and pigments.

[Urethane catalyst]
In order to accelerate the reaction between the isocyanate (B) and the polyolefin polyol (C), one or more urethanization catalysts may be used as an optional component of the release agent. As the urethanization catalyst, a catalyst used in a normal urethanization reaction can be used, for example, a tin compound such as dibutyltin dilaurate or dioctyltin dilaurate; a metal carboxylate such as zinc, cobalt, copper or bismuth; Examples thereof include amine compounds such as 4-diazabicyclo [2.2.2] octane; metal chelate compounds such as titanium and zirconium. Moreover, organic acid bismuth salt can also be used as a urethanization catalyst. Examples of the organic acid bismuth salt include alicyclic organic acids such as abietic acid, neoabietic acid, d-pimalic acid, iso-d-pimalic acid and podocarp acid, and resin acids mainly containing two or more of these. And bismuth salts of aromatic organic acids such as benzoic acid, cinnamic acid, and p-oxycinnamic acid. Among these, dibutyltin dilaurate, dioctyltin dilaurate, bismuth carboxylate and resin acid bismuth salt are preferable from the viewpoint of compatibility with the release agent component and catalytic activity.

When a urethanization catalyst is used, the amount used (ie, the content in the release agent) is preferably 0.05 to 2.0 parts by weight with respect to 100 parts by weight of the non-reactive polyolefin (A). The amount is preferably 0.1 to 1.5 parts by weight, more preferably 0.1 to 1.0 parts by weight. If this amount used is less than 0.05 parts by weight, the reaction promoting effect may not be sufficient, and if it exceeds 2.0 parts by weight, the release force of the release agent layer to be formed increases or There may be a problem that the release agent pot life is shortened.

In addition, the usage-amount of a urethanization catalyst here refers to the quantity of a urethanization catalyst only, for example, when using a commercially available urethanization catalyst solution, the quantity of only the urethanization catalyst except the amount of solvents is meant.

2. Release material The present invention also provides a release material having a substrate and a release agent layer. The release material of the present invention is characterized by having a release agent layer formed from the release agent of the present invention on at least one surface of a substrate. Hereinafter, the substrate and the release agent layer will be described in order.

[Base material]
In the present invention, the substrate is not particularly limited. However, the substrate is preferably a plastic film having a smooth surface. Examples of the plastic film include polyester films such as polyethylene terephthalate film and polybutylene terephthalate film; polyolefin films such as polyethylene film and polypropylene film. Further, paper such as kraft paper, glassine paper, and high-quality paper may be used as the base material. As the paper base material, in order to prevent excessive impregnation of the release agent into the base material, one laminated with a plastic such as polyethylene, or one subjected to sealing treatment is preferable. The base material may be subjected to a treatment such as a corona treatment, a plasma treatment, or a flame treatment in advance as necessary.

The thickness of the base material is not particularly limited and can be appropriately set according to the purpose of use. When a plastic film is used as the substrate, the thickness is usually about 12 to 250 μm, preferably 16 to 200 μm, more preferably 25 to 125 μm.

In addition, if necessary, light stabilizers such as antioxidants, ultraviolet absorbers, hindered amine light stabilizers and antistatic agents, carbon black, calcium oxide, magnesium oxide, silica, zinc oxide, titanium oxide fillers, You may mix | blend a pigment etc. with a base material.

[Release layer]
The release agent layer can be formed, for example, by dissolving the above-described release agent component in a solvent, applying the solution to a substrate, and drying. The solid content of the release agent solution is not particularly limited in the present invention, but is usually in the range of 0.1 to 5% by weight.

As long as the release agent component can be dissolved uniformly, the solvent is not particularly limited. However, since the release agent of the present invention contains the non-reactive polyolefin (A) as an essential component, the solvent is preferably a mixed solvent of only one hydrocarbon solvent, two or more hydrocarbon solvents, Alternatively, it is a mixed solvent of a hydrocarbon solvent and another solvent. When the mixed solvent is used, the content of the hydrocarbon solvent is preferably 50% by weight or more, more preferably 70% by weight or more, and more preferably 90% by weight or more in the mixed solvent. Examples of the hydrocarbon solvent include aliphatic hydrocarbons such as normal hexane and normal heptane, alicyclic hydrocarbons such as cyclohexane, and aromatic hydrocarbons such as toluene and xylene. Examples of other solvents include ketones such as methyl ethyl ketone, cyclohexanone and acetylacetone, esters such as ethyl acetate, alcohols such as methanol, ethanol and isopropyl alcohol.

The application method of the release agent solution is not particularly limited, and any known method, for example, a method using a kiss roll coater, a bead coater, a rod coater, a Meyer bar coater, a die coater, a gravure coater, or the like can be used. There is no particular limitation on the drying method, and any known method can be used. A common drying method is hot air drying. The temperature of hot air drying may vary depending on the heat resistance of the substrate, but is usually about 80 to 150 ° C.

The thickness of the release agent layer after drying is preferably 30 to 500 nm, more preferably 45 to 400 nm, and still more preferably 60 to 300 nm. When this thickness is less than 30 nm, the release force of the release agent layer may be too high. Conversely, when it exceeds 500 nm, the substrate and the release agent layer that come into contact with each other when the release material is wound into a roll shape, May cause a problem that it becomes easy to block, and a problem that the peeling force of the release agent layer becomes high.

In the release material, another layer may exist between the release agent layer and the substrate as long as the release agent layer is present on the outermost surface. However, the release agent layer is preferably formed directly on the substrate.

3. The present invention also provides a pressure-sensitive adhesive tape having the pressure-sensitive adhesive layer and the release material of the present invention, wherein the pressure-sensitive adhesive layer and the release agent layer of the mold release material are in contact with each other.

There is no particular limitation on the pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer. Examples of the pressure-sensitive adhesive include a rubber-based pressure-sensitive adhesive, an acrylic pressure-sensitive adhesive, and a polyester-based pressure-sensitive adhesive. Among these, acrylic adhesives and polyester adhesives are preferred. The pressure-sensitive adhesive tape with a release material having a pressure-sensitive adhesive layer formed using an acrylic pressure-sensitive adhesive and a polyester-based pressure-sensitive adhesive exhibits stable releasability.

The acrylic pressure-sensitive adhesive is mainly composed of an acrylic polymer obtained by a conventional polymerization method such as a solution polymerization method, an emulsion polymerization method, a UV polymerization method, and, as necessary, a crosslinking agent, a tackifier, a softener, It can be prepared by adding various additives such as anti-aging agents and fillers.

As the acrylic polymer, for example, alkyl (meth) acrylate such as butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate is used as a main component. -Hydroxy group-containing monomers such as hydroxyethyl (meth) acrylate, carboxy group-containing monomers such as (meth) acrylic acid, styrene monomers such as styrene, vinyl esters such as vinyl acetate, etc. Examples thereof include a copolymer of a monomer mixture to which a monomer is added.

As the polyester-based pressure-sensitive adhesive, a polyester-based polymer having an aliphatic polyol diol (for example, a carbonate diol obtained by reaction of a diol component such as butanediol and a carbonate compound such as ethylene carbonate) as an essential polyol component is used. Examples include a pressure-sensitive adhesive as a main ingredient.

The pressure-sensitive adhesive layer can be formed, for example, by applying a pressure-sensitive adhesive solution onto a substrate and drying it. Alternatively, a pressure-sensitive adhesive layer may be formed by applying a pressure-sensitive adhesive solution on a base material different from the base material of the release material and drying it, and then bonding this to the release agent layer of the release material. Furthermore, you may form the adhesive layer of a mold release material by bonding a commercially available adhesive tape to the release agent layer of a mold release material. The thickness of the pressure-sensitive adhesive layer can be appropriately selected in consideration of adhesiveness and the like, and is preferably 3 to 100 μm, more preferably 5 to 90 μm, and still more preferably 10 to 80 μm.

4). Adhesive tape with release agent layer An adhesive tape with a release agent layer can also be produced by forming an adhesive layer on the substrate side of the release material of the present invention. Hereinafter, the release agent layer of this aspect may be referred to as a “back treatment layer”, and the adhesive tape of this aspect may be referred to as “back treatment layer-attached adhesive tape”.

The backside treatment layer-attached adhesive tape may be either rolled up or laminated. In any form, the pressure-sensitive adhesive layer is protected by the back treatment layer.

In the pressure-sensitive adhesive tape with a back treatment layer, the pressure-sensitive adhesive layer and the back treatment layer may both be formed directly on the substrate, and another layer is formed between these layers and the substrate. It may be. However, both the pressure-sensitive adhesive layer and the back treatment layer must be present on the outermost surface. By doing this, when the pressure-sensitive adhesive tape is wound in a roll shape or when the pressure-sensitive adhesive tape in the form of a sheet is laminated, the back treatment layer can be in contact with the pressure-sensitive adhesive layer to protect it. it can. In addition, it is preferable that both the pressure-sensitive adhesive layer and the back treatment layer are directly formed on the substrate.

The pressure-sensitive adhesive used for forming the pressure-sensitive adhesive layer of the pressure-sensitive adhesive tape with the back treatment layer is not particularly limited. As an adhesive for this, what was demonstrated with the adhesive tape with a mold release material etc. are mentioned, for example. Moreover, the formation method of an adhesive layer can also employ | adopt the method similar to what was demonstrated with the adhesive tape with a mold release material.

As the method for forming the back treatment layer, the same method as described for the pressure-sensitive adhesive tape with a release material can be employed. The thickness of the back treatment layer is preferably 30 to 500 nm, more preferably 45 to 400 nm, and still more preferably 60 to 300 nm, from the viewpoint of peeling force.

5. Physical properties, properties, etc. The physical properties, properties, etc. in this specification are measured values by the following methods.
(1) Density This is a value measured according to ASTM D1505.
(2) Melt flow rate (230 ° C)
It is a value measured according to ASTM D1238.
(3) Number average molecular weight It is the value measured based on ASTM D2503.
(4) Hydroxyl value A value measured in accordance with JIS K1557: 1970.

Hereinafter, the present invention will be specifically described with reference to Reference Examples, Examples and Comparative Examples, but these do not limit the present invention. In the following, “part” and “%” represent “part by weight” and “% by weight”, respectively, unless otherwise specified.

1. Release agent component The release agent components used in Reference Examples, Examples and Comparative Examples are described below.

(1) Ethylene-based α-olefin copolymer (A-1)
Tuffmer P-0280 (ethylene-propylene copolymer (ethylene: 87 mol%, propylene: 13 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 5.4 g / 10 min, density: 0.87 g / cm ³ , Tensile elastic modulus at 23 ° C .: 5.1 MPa, tensile fracture stress at 23 ° C .: 3.3 MPa)
TAFMER A-3570S (ethylene-1-butene copolymer (ethylene: 85 mol%, 1-butene: 15 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 65 g / 10 min, density: 0.87 g / cm ³ , tensile elastic modulus at 23 ° C .: 3.5 MPa, tensile fracture stress at 23 ° C .: 2.1 MPa)

(2) Propylene α-olefin copolymer (A-2)
TAFMER XM-7070 (propylene-1-butene copolymer (propylene: 74 mol%, 1-butene: 26 mol%), manufactured by Mitsui Chemicals, MFR (230 ° C.): 7 g / 10 min, density: 0.884 g / cm ³ )

(3) Other copolymer Hibler 7311 (polyblock block-hydrogenated vinyl / polyisoprene block-polystyrene block triblock copolymer, manufactured by Kuraray Co., Ltd., MFR (230 ° C.): 2 g / 10 min, density: 0.89 g / Cm ³ )

(4) Isocyanate (B)
Coronate L (75% ethyl acetate solution of trimethylolpropane adduct of tolylene diisocyanate, number of isocyanate groups in one molecule: 3, manufactured by Nippon Polyurethane)

(5) Polyolefin polyol (C)
Epol (hydroxyl-terminated liquid hydrogenated polyisoprene, Mn: 2500, hydroxyl value: 50.5 mg KOH / g, manufactured by Idemitsu Kosan Co., Ltd.)

(6) Urethane catalyst dibutyltin dilaurate (IV) (manufactured by Wako Pure Chemical Industries, Ltd., dibutyltin dilaurate)

2. Preparation of release agent The release agent component was dissolved in toluene in the number of parts shown in Table 1 to prepare a release agent solution having a solid content of 1.5%.

3. Formation of release agent layer (preparation of release material)
The prepared release agent was applied to a 38 μm thick polyester film using Mayer bar # 6, and then heated with a hot air dryer at 130 ° C. for 1 minute to obtain a release material. The thickness of the release agent layer of the obtained release material was about 150 nm.

4). Characteristic evaluation The characteristics (base material adhesion and state peeling force) of the release agent layer of the obtained release material were evaluated by the following methods. The evaluation results are shown in Table 1.

(1) Substrate adhesion The state when the surface of the release agent layer was rubbed 3 times with a finger was determined according to the following criteria.
◯: There is no change or the surface becomes whitish and cloudy, but the release agent layer does not fall off.
X: The release agent layer falls off and scraps are generated when the eraser is rubbed, and the substrate is exposed.

(2) Normal peel strength Acrylic adhesive tape No. 25 mm wide 31B (manufactured by Nitto Denko Corporation) was bonded to the surface of the release agent layer using a hand roller and stored at 23 ° C. for 24 hours, and then the mold release material was 3.0 m / min in the 180 ° direction with a tensile tester. The normal peel strength was measured in an atmosphere at 23 ° C.

As shown in Table 1, when the propylene-based α-olefin copolymer (A-2) is added to the release agent, the release force of the formed release agent layer is changed to the propylene-based α-olefin copolymer ( It rises according to the added amount of A-2). However, if another copolymer (polystyrene block-hydrogenated vinyl / polyisoprene block-polystyrene block triblock copolymer) is added instead of the propylene-based α-olefin copolymer (A-2), it is added. Even if the amount is small, the release force of the release agent layer increases abruptly, and there is no correlation between the addition amount of the other copolymer and the release force. From these results, it can be seen that the release force of the release agent layer to be formed can be easily adjusted by adjusting the addition amount of the propylene-based α-olefin copolymer (A-2).

According to the method for producing a release agent of the present invention, the release force of the release agent can be easily adjusted. The release agent obtained from the production method of the present invention, and the release material and adhesive tape produced using this release agent can be suitably used for various applications such as those related to electronic components.

Claims

A method for producing a release agent containing non-reactive polyolefin (A), isocyanate (B) and polyolefin polyol (C),
The amount of non-reactive polyolefin (A) used is 80 parts by weight or more in 100 parts by weight of the obtained release agent,
The non-reactive polyolefin (A) includes an ethylene-based α-olefin copolymer (A-1) in which the amount of ethylene constitutional units in the copolymer is 50 mol% or more, and the amount of propylene constitutional units in the copolymer. Containing a propylene-based α-olefin copolymer (A-2) of more than 50 mol%,
The ethylene-based α-olefin copolymer (A-1) has a tensile modulus at 23 ° C. of 10 MPa or less, and a tensile fracture stress at 23 ° C. of 8 MPa or less.
The amount of the ethylene-based α-olefin copolymer (A-1) used is 90 to 99.9 parts by weight in 100 parts by weight of the non-reactive polyolefin (A),
A method wherein the amount of the propylene-based α-olefin copolymer (A-2) used is 0.1 to 10 parts by weight per 100 parts by weight of the non-reactive polyolefin (A).
The method according to claim 1, wherein the isocyanate (B) is a polyisocyanate having three or more isocyanate groups in one molecule.
The method according to claim 2, wherein the polyisocyanate is at least one selected from the group consisting of an aromatic polyisocyanate and an alicyclic polyisocyanate.
The method according to claim 3, wherein the polyisocyanate is at least one selected from the group consisting of an aromatic diisocyanate polyhydric alcohol adduct and an alicyclic diisocyanate polyhydric alcohol adduct.
The method according to any one of claims 1 to 4, wherein the amount of the isocyanate (B) used is 0.5 to 20 parts by weight with respect to 100 parts by weight of the non-reactive polyolefin (A).
The method according to any one of claims 1 to 5, wherein the polyolefin polyol (C) has a number average molecular weight of 1500 to 50000.
A release agent produced by the method according to any one of claims 1 to 6.
A release material having a base material and a release agent layer,
A mold release material having a release agent layer formed from the release agent according to claim 7 on at least one side of the substrate.
An adhesive tape having an adhesive layer and the release material according to claim 8,
An adhesive tape in which the adhesive layer and the release agent layer of the release material are in contact.
A pressure-sensitive adhesive tape having a base material, a pressure-sensitive adhesive layer and a release agent layer;
A release agent layer formed from the release agent according to claim 7 is provided on one side of the substrate,
A pressure-sensitive adhesive tape having a pressure-sensitive adhesive layer on the other surface of a substrate on which a release agent layer is not formed.