JP2017056631A - Release film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a release film having good release properties.SOLUTION: There is provided a release film obtained by laminating a release layer containing 0.1 to 90 wt.% of a silylated polyolefin having a silicone part represented by the formula (1) and a polyolefin part and a thermoplastic resin such as a polyolefin without containing a silicone part in the constitutional unit, for example, on a substrate made of resin such as a polyolefin, a polyester, a polyamide, a polyimide and a polyethersulfone and a substrate made of paper such as a corrugated board base paper as resins used for a substrate layer. (Ato Aeach independently represent a polyolefin chain or a hydrocarbon group having 1 to 10 carbon atoms; Rs each independently represent a hydrocarbon group having 1 to 10 carbon atoms; m represents an integer of 1 to 10000; at least one of Ato Arepresents a polyolefin chain.)SELECTED DRAWING: None

Description

  The present invention relates to a release film.

The release film is obtained by forming a release layer on a film of paper or resin that becomes a base material layer.
The release film may be referred to as release paper, release sheet, or the like.
The release film is affixed to the product or the adhesive surface for the purpose of protecting various products, protecting the adhesive surface, assisting the manufacturing process of various products, etc., and is peeled off from the applied surface during work or use of the product. (For example, Patent Document 1)
The process film is a release film used in the production process of various products, and may be referred to as a process release film, a process paper, a process release paper, a process sheet, or a process release sheet.

JP 2005-138339 A

In recent years, from the viewpoints of shortening the manufacturing process, improving workability, improving product yield, and the like, there is a demand for a release film with more excellent releasability (releasability).
This invention is made | formed in view of the said situation, and provides a peeling film with favorable peelability.

That is, according to this invention, the peeling film shown below is provided.
[1] A release film having a base material layer (A) and a release layer (B) containing a silylated polyolefin.
[2] The release film according to [1], wherein the base material layer (A) is a paper or resin film.
[3] The release film according to [1] or [2], wherein the silylated polyolefin is a silylated polyolefin represented by the following formula (1).

(In the formula (1), A ¹ , A ² and A ³ are each independently a polyolefin chain or a hydrocarbon group having 1 to 10 carbon atoms. R is a hydrocarbon group having 1 to 10 carbon atoms. Each R may be the same or different, m is an integer of 1 to 10,000, and when a plurality of A ³ are present, each A ³ may be the same or different, provided that A ¹ , A ² , A ³ represents at least one polyolefin chain.)

[4] The release film according to any one of [1] to [3], wherein the release layer (B) is composed of a resin composition containing a thermoplastic resin and a silylated polyolefin.
[5] The content of the silylated polyolefin in the resin composition constituting the release layer (B) is 0.1 wt% or more and 90 wt% when the total of the thermoplastic resin and silylated polyolefin is 100 wt%. % Or less, the release film according to the above [4].
[6] The release film according to the above [4] or [5], wherein the resin composition constituting the release layer (B) is a resin composition with less generation of eyes when molded.
[7] The release film according to any one of [1] to [6], wherein the release film is a process film.

  The release film of the present invention has good peelability.

Below, the peeling film of this invention is demonstrated. In addition, unless otherwise indicated, the symbol "ab" which shows the numerical range in a sentence shall express from a to b or less.
The release film of the present invention includes a base layer (A) and a release layer (B) containing silylated polyolefin.

[Base material layer (A)]
The material of the base material layer (A) is not particularly limited, and a resin base material, a paper base material, or the like can be used. Examples of the resin used for the base material layer include polyolefins such as polyethylene and polypropylene, polyesters such as polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, and polyethylene naphthalate, polyamides, polyimides, and polyethersulfones. Examples of paper base materials include cardboard, yellow paper, and white paperboard, various base papers, paper, art paper, printing paper, glassine paper, kraft paper, synthetic paper, synthetic fiber paper, coated paper, Japanese paper etc. can be mentioned.
Moreover, cloth, a nonwoven fabric, etc. can be used as a base material.

[Peeling layer (B)]
The release layer (B) contains silylated polyolefin.

(Silylated polyolefin)
The silylated polyolefin used for the layer (B) may have any structure as long as it has a silicone part and a polyolefin part, but preferably has a structure represented by the following formula (1).

(In the above formula (1), A ¹ , A ² and A ³ are each independently a polyolefin chain or a hydrocarbon group having 1 to 10 carbon atoms. R is a hydrocarbon group having 1 to 10 carbon atoms. Each R may be the same or different, m is an integer of 1 to 10,000, and when a plurality of A ³ are present, each A ³ may be the same or different, provided that A ¹ , A ² , A ³ represents at least one polyolefin chain.)

The polyolefin chain in A ¹ , A ² and A ³ is a polymer chain including a structural unit derived from an olefin having 2 to 50 carbon atoms, preferably 2 to 20 carbon atoms, for example.
Specific examples of the olefin having 2 to 50 carbon atoms include ethylene and an α-olefin having 3 to 50 carbon atoms (propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4 -Methyl-1-pentene, 3-methyl-1-pentene, 3,4-dimethyl-1-pentene, 4-methyl-1-hexene, 3-ethyl-1-pentene, 3-ethyl-4-methyl-1 -Pentene, 3,4-dimethyl-1-hexene, 4-methyl-1-heptene, 3,4-dimethyl-1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene 1-octadecene, 1-eicocene, vinylcyclohexane, etc.).

Among these, ethylene and an α-olefin having 3 to 12 carbon atoms are preferable, ethylene and an α-olefin having 3 to 8 carbon atoms are more preferable, and ethylene is particularly preferable.
The polyolefin chain may be a homopolymer chain or a copolymer chain.

  Especially, the polymer chain comprised only from C2-C50 olefin chosen from ethylene and C3-C50 alpha olefin is preferable, Furthermore, ethylene homopolymer chain, propylene homopolymer chain, Alternatively, an ethylene / C3-C20 α-olefin copolymer chain is preferred. In the copolymer chain of ethylene / C3-C20 α-olefin, when all the structural units are 100 mol%, the structural unit derived from C3-C20 α-olefin exceeds, for example, 0 mol%. It can also be 20 mol% or less, and can also be over 0 mol% and 10 mol% or less.

  Moreover, the said polyolefin chain may also contain the structural unit derived from another olefin as needed. Other olefins include olefins containing an internal double bond such as cis-2-butene; vinylidene compounds such as isobutene; aryl vinyl compounds such as styrene; arylvinylidene compounds such as α-methylstyrene; and functionalities such as methyl methacrylate. Group-substituted vinylidene compounds; aliphatic cyclic olefins containing internal double bonds such as 5-methyl-2-norbornene, tetracyclododecene, cyclopentadiene, dicyclopentadiene; cyclic olefins containing an aromatic ring such as indene; butadiene, Examples thereof include linear or cyclic polyenes such as isoprene, ethylidene norbornene and vinyl norbornene.

  The content of structural units derived from other olefins is preferably 0 to 10 mol%, more preferably 0 to 5 mol%, assuming that all the structural units constituting the polyolefin chain are 100 mol%.

  The polyolefin chain preferably has a number average molecular weight of 100 or more and 500,000 or less, more preferably 200 or more and 100,000 or less, further preferably 500 or more and 50,000 or less, and more preferably 700 or more. 10,000 or less is more preferable.

  The polyolefin chain preferably has a molecular weight distribution (Mw / Mn) determined by the following GPC method in the range of 1.1 to 3.0.

GPC measurement method:
GPC measurement can be performed at a temperature of 140 ° C. using orthodichlorobenzene as a solvent, and analytical values (weight average molecular weight (Mw), number average molecular weight (Mn) and Mw / Mn) can be obtained as polyethylene conversion values. .
The measurement can be performed under the following conditions. The molecular weight can be determined based on the following conversion method by creating a calibration curve using commercially available monodisperse standard polystyrene.
Apparatus: Gel permeation chromatograph Alliance GPC2000 (manufactured by Waters)
Solvent: o-dichlorobenzene column: TSKgel column (manufactured by Tosoh Corporation) x 4
Flow rate: 1.0 ml / min Sample: 0.15 mg / mLo-dichlorobenzene solution temperature: 140 ° C.
Molecular weight conversion: PS conversion / General calibration method

In addition, the coefficient of the Mark-Houwink viscosity formula shown below can be used for calculation of general-purpose calibration.
Coefficient of polystyrene (PS): KPS = 1.38 × 10 ⁻⁴ , aPS = 0.70
Coefficient of polyethylene (PE): KPE = 0.06 × 10 ⁻⁴ , aPE = 0.70

In the above A ¹ , A ² , A ³ and R, examples of the hydrocarbon group having 1 to 10 carbon atoms include an alkyl group, an arylalkyl group, an alkenyl group, and an aryl group.
Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, hexyl group, 2-ethylhexyl group, octyl group, decyl group, and octadecyl group. A linear or branched alkyl group; a cycloalkyl group such as a cyclopentyl group, a cyclohexyl group and a norbornyl group;
Examples of the arylalkyl group include a benzyl group, a phenylethyl group, and a phenylpropyl group.

Examples of the alkenyl group include a vinyl group, a propenyl group, and a cyclohexenyl group.
Examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, a trimethylphenyl group, an ethylphenyl group, a propylphenyl group, and a naphthyl group.
In the above formula (1), m is an integer of 1 to 10,000. m is preferably 5 or more, and more preferably 10 or more. Further, m is preferably 1,000 or less, more preferably 300 or less, and even more preferably 50 or less.

The above A ¹ , A ² , single or plural A ³ may be all polyolefin chains, or some groups may be polyolefin chains and others may be hydrocarbon groups having 1 to 10 carbon atoms. .

In the above formula (1), m is equal to or greater than 2, when at least one of A ³ that is different from the other A ^3, but plural kinds of the following units are present, not particularly limited in its aligned sequence, block Or random.

As said formula (1), the structure represented by following (1A), (1B) or (1C) is preferable, and (1A) is more preferable among these.
(1A) In the above formula (1), A ¹ and A ² are polyolefin chains, and A ³ is a hydrocarbon group having 1 to 10 carbon atoms.
(1B) In the above formula (1), one of A ¹ and A ² is a polyolefin chain, the other is a hydrocarbon group having 1 to 10 carbon atoms, and A ³ is a hydrocarbon group having 1 to 10 carbon atoms. There is a structure.
(1C) In the above formula (1), A ¹ and A ² are hydrocarbon groups having 1 to 10 carbon atoms, and at least one of A ³ is a polyolefin chain.
In the silylated polyolefin according to the present invention, the silicone part / polyolefin part (weight ratio) is not particularly limited, but is preferably 5/95 to 99/1, and more preferably 10/90 to 95, for example. / 5.
Although the manufacturing method of the silylated polyolefin based on this invention is not specifically limited, For example, it can manufacture by the method described in paragraphs 0089-0145, paragraphs 0196-0207, etc. of WO2012 / 098865 gazette.

(Thermoplastic resin)
The material constituting the release layer (B) may be only silylated polyolefin, but may contain other components such as a thermoplastic resin and a thermosetting resin. Especially, it is preferable to be comprised from the resin composition containing a thermoplastic resin and the said silylated polyolefin.
Examples of the thermoplastic resin include polyolefin, polyvinyl chloride, polyvinylidene chloride, ethylene / vinyl acetate copolymer, ethylene / methacrylic acid copolymer, polyester such as polyethylene terephthalate, polycarbonate, polyamide, ABS resin, polyacetal resin, polyimide , Polyurethane, polylactic acid and the like.
Of these, polyolefin is preferable. Here, the polyolefin refers to a polyolefin that does not contain a silicone moiety in the structural unit. Examples of the polyolefin include ethylene homopolymer or copolymer and propylene homopolymer or copolymer.

(Thermoplastic resin composition)
The resin composition containing the thermoplastic resin forming the release layer (B) and the silylated polyolefin has a silylated polyolefin content of 0.00 when the total of the thermoplastic resin and the silylated polyolefin is 100% by weight. It is preferably 1 to 90% by weight, more preferably 0.1 to 50% by weight, and more preferably 0.3 to 30% by weight.

  The resin composition may be composed of only a thermoplastic resin and a silylated polyolefin, but if desired, within a range not impairing the object of the present invention, for example, a total of 100 parts by weight of the thermoplastic resin and the silylated polyolefin. In the range of 10 parts by weight or less, other resins, additives and the like can be further contained.

  Each component can be melt-kneaded using a known method, for example, a single-screw or twin-screw extruder, a kneader, a Henschel mixer, a Banbury mixer, a tumbler mixer, etc., and used as pelletized as necessary. You can also.

Further, a master batch having a high concentration of silylated polyolefin may be prepared, and the master batch may be diluted with a thermoplastic resin.
The silylated polyolefin is excellent as a release agent. Moreover, it is difficult to bleed out from the surface of the release layer.

  Furthermore, it is surmised that the silylated polyolefin has an effect of suppressing generation of eyes when molding a thermoplastic resin composition containing the silylated polyolefin. Therefore, not only in the production of a release film, but also in the melt molding represented by, for example, extrusion molding and injection molding, by adding the silylated polyolefin to the raw material resin, the generation of eyes can be suppressed and the vicinity of the exit of the molding machine It can be expected that the frequency at which the eye spear adheres to the surface decreases. The addition amount of silylated polyolefin is not particularly limited.

(Resin composition containing thermosetting resin)
Moreover, as a peeling layer (B) of this invention, the peeling layer (B) comprised from the resin composition containing the said silylated polyolefin and a thermosetting resin is also illustrated.

Examples of the thermosetting resin include epoxy resin, thermosetting unsaturated polyester resin, phenol resin, and thermosetting polyolefin (DCPD resin, polybutadiene resin, etc.).
When the total of the thermosetting resin and the silylated polyolefin is 100% by weight, the content of the silylated polyolefin is preferably 0.1 to 90% by weight, more preferably 0.1 to 50% by weight, More preferably, it is 3 to 30% by weight.
A resin composition containing a silylated polyolefin and a thermosetting resin can be produced by a conventionally known method.

[Peeling film]
The release film according to the present invention has the substrate layer (A) and the release layer (B).
The release film may be only the base layer (A) and the release layer (B), but other layers may be provided as desired. The release layer (B) may be provided on one side of the base material layer (A) or on both sides. Alternatively, a release layer (B) may be provided on one side of the base material layer (A), and a release layer different from the release layer (B) may be provided on the opposite side. When the release layer is provided on both sides of the base material layer, the peel force may or may not be different.

The base material layer (A) and the release layer (B) may be adjacent to each other, and other layers may be interposed between the base material layer (A) and the release layer (B).
Other layers are not particularly limited, but for example, adhesive films, adhesive layers, colored layers, printed layers, antistatic layers, reinforcing layers, sealing layers, anchor coat layers, anti-curl layers, and other uses for release films The layer according to is mentioned.

  For example, the release film may be a method of co-extruding the material of the base layer (A) and the material of the release layer (B); a method of extruding the material of the release layer (B) on the base layer (A) A method of bonding the base layer (A) and the release layer (B); a method of coating the base layer (A) by dissolving or dispersing the material forming the release layer (B) in an appropriate solvent. It is done.

Even when it has other layers, it is possible to produce a release film by combining any one or a combination of lamination methods selected from extrusion methods, coextrusion methods, bonding methods, coating methods, and other methods. It is.
There is no restriction | limiting in particular in the shape of a peeling film. The release film may be, for example, flat or tape. The release film may be folded or rolled.
The thickness and molding conditions of each layer can be set as appropriate.
The release film may be stretched.

In the stretching treatment, the base layer (A) may be stretched and then the release layer (B) may be provided, or the laminate including the base layer (A) and the release layer (B) may be stretched. Also good.
As the stretching method, any of stretching methods of uniaxial stretching in the vertical direction (MD direction); uniaxial stretching in the horizontal direction (TD direction); sequential biaxial stretching; and simultaneous biaxial stretching may be adopted.
Examples of the stretching device include a roll and a tenter.

The stretching temperature and the stretching ratio are appropriately set. If necessary, a heat treatment can be performed at an arbitrary temperature and time after stretching.
The release film can be provided with irregularities such as embossing.
The unevenness may be applied to the base material layer (A) before the release layer (B) is provided or after the release layer (B) is provided.

(Use)
The release film of the present invention can be used in a wide range of fields such as optical materials, electronic materials, building materials, automobiles, medical care, medicines, cosmetics, foods, resin molding, agriculture, and daily necessities.
Although the specific use example of the peeling film of this invention is described in following Table 1, it is not limited to these.

    EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention further more concretely, the scope of the present invention is not limited to these Examples.

[Synthesis Example 1]
According to the method described in Synthesis Example 2 of International Publication No. 2012/098865, a one-end vinyl group-containing ethylene polymer (P-1) was synthesized. The physical properties of this one-end vinyl group-containing ethylene polymer (P-1) (single unit) were as follows.
Melting point (Tm) 127 ° C
Mw = 4800, Mn = 2087, Mw / Mn = 2.3 (GPC)
Terminal unsaturation 97%

[Synthesis Example 2]
A 300 ml two-necked flask was charged with 25.1 g (11.8 mmol) of the one-end vinyl group-containing ethylene polymer (P-1) obtained in [Synthesis Example 1], and the following structure was obtained under a nitrogen atmosphere. 6.2 g (5.9 mmol; equivalent to 11.8 mmol as Si—H group) of hydrosilane A (Gelest, Inc., DMS-H11) and platinum prepared according to Synthesis Example 3 of International Publication No. 2012/098865 150 μl of the catalyst composition (C-1) diluted 200-fold with hydrosilane A (1.4 × 10 ⁻⁶ mmol in terms of Pt) was charged. The reactor was set in an oil bath that had been heated to an internal temperature of 130 ° C. in advance, and stirred. The mixture was stirred in an oil bath for 6 hours and then cooled, about 200 ml of methanol was added, and the contents were taken out into a 300 ml beaker and stirred for 2 hours. Thereafter, the solid is collected by filtration and dried, whereby in formula (1), A ¹ and A ² are ethylene homopolymer chains, A ³ is a methyl group, R is a methyl group, and m is 12 33.5 g of a white solid silylated polyolefin of ˜13 was obtained. As a result of NMR analysis, the obtained silylated polyolefin had a yield of 99%, an olefin conversion rate of 100%, and an isomerization rate of 1%. The number average molecular weight analyzed by GPC was 5,000.
Hydrosilane A:
_{HSi (CH 3) 2 O -} (- Si (CH 3) 2 -O-) n -Si (CH 3) 2 H
(N = 12-13)

[Example 1]
Resin composition containing polypropylene homopolymer (melting point 159 ° C., MFR = 3 g / 10 min [ASTM D1238, 230 ° C., 2.16 kg load]) and silylated polyolefin obtained in Synthesis Example 2 in a weight ratio of 85/15 Using a product as a raw material, a 200 μm thick film was prepared using an extruder with a T-die.
To the obtained film, an adhesive tape (adhesive tape 31B manufactured by Nitto Denko Co., Ltd.) 1 reciprocating with a 2 kg roller was left for 30 minutes, then cut into a strip with a substrate width of 25 mm, and a tensile tester was used. A 180 ° peel test was performed at a speed of 300 mm / min.
The peeling force was 0.33 N / 25 mm.

[Example 2]
The same procedure as in Example 1 was performed except that the weight ratio of the polypropylene homopolymer to the silylated polyolefin was 90/10. The peeling force was 0.51 N / 25 mm.

[Comparative Example 1]
The same procedure as in Example 1 was carried out except that no silylated polyolefin was used. The peeling force was 2.1 N / 25 mm.
The above examples and comparative examples show that the layer containing silylated polyolefin has good peelability. Therefore, a release film is obtained by laminating a layer containing silylated polyolefin on a support layer (base material).

Claims (7)

A release film having a base material layer (A) and a release layer (B) containing a silylated polyolefin.   The release film according to claim 1, wherein the base material layer (A) is a paper or resin film. The release film according to claim 1 or 2, wherein the silylated polyolefin is a silylated polyolefin represented by the following formula (1).
(In the formula (1), A ¹ , A ² and A ³ are each independently a polyolefin chain or a hydrocarbon group having 1 to 10 carbon atoms. R is a hydrocarbon group having 1 to 10 carbon atoms. Each R may be the same or different, m is an integer of 1 to 10,000, and when a plurality of A ³ are present, each A ³ may be the same or different, provided that A ¹ , A ² , A ³ represents at least one polyolefin chain.) The release film according to any one of claims 1 to 3, wherein the release layer (B) is composed of a resin composition containing a thermoplastic resin and a silylated polyolefin.   The content of the silylated polyolefin in the resin composition constituting the release layer (B) is 0.1 wt% or more and 90 wt% or less when the total of the thermoplastic resin and silylated polyolefin is 100 wt%. The peeling film of Claim 4 which exists.   The release film of Claim 4 or 5 whose resin composition which comprises a peeling layer (B) is a resin composition with few generation | occurrence | production of the eyes | gear of molding at the time of shaping | molding. The release film according to any one of claims 1 to 6, wherein the release film is a process film.