JPH01149883A - Releasability-affording treating agent - Google Patents

Abstract

PURPOSE:To provide the title treating agent capable of baking at low temperatures, nonselective for substrates, also capable of forming release surface as to be able to write with e.g. a pen etc. thereon, with moderate peel strength, containing a resin having in the side chain siloxane segment. CONSTITUTION:The objective treating agent containing a resin having in the side chain siloxane segment. Preferably, said resin is selected from a group made up of polyurethane, polyurea, acrylic and vinyl resins, containing a releasability-affording substance, also in the form of an organic solvent solution.

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a releasable treatment agent, and more specifically, it is used in products using adhesives such as adhesive tapes, adhesive labels, adhesive sheets, etc. The present invention relates to a releasable treatment agent that can make the back surface of a base material such as a tape or the surface of a release paper releasable.

(Prior Art) Conventionally, as release agents used for the above purpose, polymer compounds such as acrylic acid, polyester, and polyamide compounds with long-chain alkyl groups bonded to them and organopolysiloxane compounds have been known. It is used to form a release surface on the back of an adhesive tape or adhesive sheet or on the surface of release paper.

Among these, organopolysiloxane compounds have excellent properties such as releasability and residual adhesiveness.

(Problems to be Solved by the Invention) Conventional organopolysiloxane compounds have the above characteristics, but their peeling strength is not adequate, and they require high-temperature baking when applied to a base material. There was a problem that it could not be used for material films. Further, depending on the base material, the adhesion to the base material is insufficient, and there is a drawback that it cannot be used for many types of base materials.

Furthermore, because the critical surface tension of removable polysiloxane compounds is small, it is difficult to write on the releasable surface, and repellent development often occurs when pressure-sensitive or heat-sensitive adhesives are applied to the releasable surface. However, there was a problem that a good coating surface could not be formed.

Therefore, an object of the present invention is to provide a releasable treatment agent that can be baked at low temperatures and can be applied to thermoplastic resin films and the like.

Another object of the present invention is to have no selectivity to the base material;
An object of the present invention is to provide a releasable treatment agent capable of forming a releasable surface on any base material.

Yet another object of the present invention is to provide a releasable treatment agent that can form a releasable surface on which water-based ink or oil-based ink can be written.

(Means for solving problems) The above objects are achieved by the present invention as described below.

That is, the present invention is a releasable treatment agent characterized by containing a resin having a siloxane segment in its side chain.

(Function) By using a resin with a siloxane segment in its side chain, it can be baked at low temperatures and has no selectivity to the base material.
In addition, it is possible to form a release surface that can be written on with a pen or the like and has an appropriate release force.

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments.

The resin having a siloxane segment used in the present invention refers to a siloxane compound having one or more reactive groups in the molecule, such as an amino group, an epoxy group, a hydroxyl group, a mercapto group, a carboxyl group, etc. It is obtained by modifying a resin having a group capable of reacting with these reactive groups at the end or middle of the main chain.

For example, specifically, the following method is preferably used.

(1) When the reactive group is an amino group, this amino group is used to react with a resin having a carboxylic acid group, acid anhydride group, isocyanate group, epoxy group, etc. at the end or in the middle of the main 3n. .

(2) When the reactive group is an epoxy group, this epoxy group is used to react with a resin having a carboxylic acid group, acid anhydride group, hydroxyl group, amino group, etc. at the end or middle of the main chain.

(3) When the reactive group is a hydroxyl group or a mercapto group,
A method using these groups to react with a resin having a carboxylic acid group, acid anhydride group, isocyanate group, epoxy group, etc. at the end or middle of the main chain.

(4) When the reactive group is a carboxyl group, this group is used to react with a resin having a hydroxyl group, isocyanate group, epoxy group, amino group, etc. at the end or in the middle of the main chain. 'Resins having the above-mentioned reactive groups include, for example, polyurethane resins, polyurea resins, polyurethane polyurea resins, acrylic resins, copolymers of olefins and acrylic monomers, partially saponified polyvinyl acetate, vinyl acetate and other Saponified copolymer with Chitsuma, epoxy resin,
Any conventionally known reactive resin such as polyamide resin, polynisder resin, cellulose resin, etc. can be used.

As the reactive polysiloxane compound used for modifying the various resins mentioned above, any conventionally known compounds can be used, and preferred examples include the following compounds.

(1) Amine-modified silicone oil (■-1 to 10, n=2 to 10, R=C113 or OC+1.) (m=I to 10, n=2 to 10, R=
CI+3 or OCH3) (m-0 to 200) (n=2 to 10) (branch point -2 to 3, former lower alkyl group, 1=2 to 2
QO, m=2 to 2QO, n=2 to 200) (n
-1 to 200, R-lower alkyl group) (2) Epoxy-modified silicone oil (n-1 to 200) (m=] to 10, n=2 to 10) (Rho 1 to 200) (branch point -2 to 3, R = lower alkyl group, 1 = 2 to 200, m = 2 to 200, n = 2 to 20
0) (n = 1 to) 0) (m = 1 to 10, n = 2 to 10) (3) Alcohol-modified silicone oil (n = 1 to 200) (m-1 to 10, n = 2 to 10 ) (m=0 to 50, n=0 to 200)? 113 (1=1 to 10, m=10 to 200, n=1 to 5) (n-1 to 200, R-lower alkyl) (4
) Mercapto-modified silicone oil (m-1 to 10,
n = 2 to 10) (n-2 to 10) (branch point = 2 to 3, R = lower alkyl group, 1 = 2 to 200, m = 2 to 200, n = 2 to 2
00) (n-1 to 200, R = lower alkyl group) (
5) Carboxyl-modified silicone oil (m=l to 1
0, n = 2 to 10) (n-1 to 200) (branch point -2 to 3, R-lower alkyl group, 1 = 2 to 200, m = 2 to 200, n = 2 to 20
0) (n=1 to 200, R-lower alkyl group) The polysiloxane compounds having the above reactive groups are examples of preferred compounds in the present invention, and the present invention is limited to these examples. Rather, the above-mentioned exemplified compounds and other compounds are currently commercially available and can be easily obtained from the market, and any of them can be conveniently used in the present invention.

Furthermore, an intermediate obtained by reacting a reactive compound as described above and a polyisocyanate as described below such that at least one of the reactive group of the polysiloxane compound or the incyanate group of the polyisocyanate group remains, such as ,2
An intermediate obtained by reacting a functional polysiloxane compound and a polyfunctional polyisocyanate enriched with incyanate groups, or conversely by reacting a polysiloxane compound with reactive groups in the form of ridges, can also be used.

Furthermore, when the reactive group of the polysiloxane compound is a hydroxyl group, amine group, carboxyl group, epoxy group, etc., a polyester polyol obtained by reacting with a polyol, a chain extender, or a polyvalent carboxylic acid or polyvalent amine, which will be described later, Polyamide polyamines, polyether polyols, etc. can also be used in the same manner.

Among the various resins having polysiloxane bonds as described above, particularly preferred in the present invention are polyurethane resins and/or polyurea resins, which will be explained in more detail using polyurethane resins as a representative example.

The polyurethane resin having a siloxane segment in its side chain is preferably prepared in one form from the reactive siloxane compound and isocyanate compound during or after preparing the polyurethane resin by reacting a polyol, a polyisocyanate, and a chain extender. It can be obtained by preparing an intermediate having an incyanate group and reacting it with a polyurethane resin.

As the polyol for polyurethane, any conventionally known polyol for polyurethane can be used, for example,
Preferably, the terminal group is a hydroxyl group and the molecular weight is 3.
00 to 4,000 polyethylene adipate, polyethylene propylene adipate, polyethylene butylene adipate, polydiethylene adipate, polybutylene adipate, polyethylene succinate, polybutylene succinate, polyethylene sebacate, polybutylene sebacate, polytetramethylene ether glycol , poly0-caprolactone diol, polyhexamethylene adipate, carbonate polyol, polypropylene glycol, and those containing an appropriate amount of polyoxyethylene chains in the above polyols.

As the organic polyisocyanate, any conventionally known organic polyisocyanate can be used. For example, a preferred example is 4,4'-diphenylmethane diisocyanate (MDI).
), water-added MDI, isophorone diisocyanate, 1.3-xylylene diisocyanate, 1.4-xylylene diisocyanate, 2.4-tolylene diisocyanate, 2.6-tolylene diisocyanate, 1.5-naphthalene diisocyanate, m- There are phenylene diisocyanate, p-phenylene diisocyanate, etc., or urethane prepolymers obtained by reacting these organic polyisocyanates with low molecular weight polyols or polyamines to form terminal incyanates can also be used. .

Any conventionally known chain extender can be used, but preferred ones include ethylene glycol, propylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, and ethylenediamine. , 1,2-propylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, inphoroncyamine, m-xylylenediamine, hydrazine, water, and the like.

Any of the polyurethane resins containing +T polysiloxane segments in the side chains obtained from the above-mentioned materials can be used in the present invention, but preferred ones include polysiloxane segments containing about 0.2 to 70% by weight in the resin. %, and the polysiloxane segment is about 0.
If the amount is less than 2% by weight, the intended purpose of the present invention will not be achieved, and if it exceeds about 70% by weight, problems such as decreased adhesion to the substrate may occur, which is not preferred.

Incidentally, the polyurea resin and the polyurethane polyurea resin can be obtained in the same manner as described above by using a polyamine in place of all or part of the polyol.

Further, preferred ones have a molecular weight of 20,000 to 500,000, and most preferred ones have a molecular weight of 20,000 to 250,000.

The polyurethane resin containing polysiloxane segments as described above can be easily obtained by conventionally known manufacturing methods. These polyurethane resins may be prepared without a solvent or in an organic solvent, but in terms of the process, by preparing them in an organic solvent where a stripping agent should be prepared, they can be prepared as is. This is advantageous because it can be used to prepare a strippable treatment agent.

Preferred organic solvents include methyl ethyl ketone, methyl-n-propyl ketone, methyl isobutyl ketone, diethyl ketone, methyl formate, ethyl formate, propyl formate, methyl acetate, ethyl acetate, butyl acetate, and acetone. , cyclohexane, tetrahydrofuran, dioxane, methanol, ethanol, isopropyl alcohol, butanol, toluene, xylene, dimethylformamide, dimethyl sulfoxide, perchloroethylene, trichlorethylene, methyl cellosolve, butyl cellosolve, cellosolve acetate, etc. can also be used. Of course, the above organic solvents can also be used as mixed organic solvents.

By preparing a polyurethane resin in such an organic solvent, a polyurethane resin solution having polysiloxane segments can be obtained, or the solid content can be reduced to about 5 to 60% by weight by addition or removal of the same or lower solvent. It is convenient to have a range. In the present invention, the polyurethane resin may be sufficiently dissolved in an organic solvent, or may be a dispersion in which it is partially or completely precipitated (hereinafter simply referred to as a solution).

The above-mentioned polyurethane resin solution itself is the release treatment agent of the present invention, and can be used as it is, and may also be supplemented with various additives such as colorants, crosslinking agents, stabilizers, fillers, etc. can be added arbitrarily.

In particular, as a type of additive, conventionally known mold release substances such as wood flour, talc, silica, boron nitride, alumina, polyethylene resin powder, hexagonal amine resin powder, silicone resin powder, melamine resin powder, fluororesin powder, phenol Resin powder or the like may be added in a range of 0 to 200 parts by weight per 100 parts by weight of the siloxane segment-containing resin. Furthermore, general thermosetting resins such as thermosetting resins and thermosetting resins can also be used as additives.

The above examples are mainly explanations of polyurethane resins, but of course, resins other than polyurethane resins can also be treated in the same manner by introducing siloxane segments as side chains into the resins and using them as release components. It can be used in the present invention.

(Effects) According to the present invention as described above, by using a resin having a siloxane segment in the side chain, it is possible to bake at a low temperature (=j), there is no selectivity with respect to the base material, and it is possible to write with a pen or the like and has a moderate It is possible to form a release surface that has release force.

(Example) Next, the present invention will be specifically described with reference to Reference Examples, Examples, and Comparative Examples. It should be noted that unless otherwise specified, the terms in the text or % are based on weight.

Reference Example 1 (Production Example of Intermediate) 1 mole of trimedylolbroban and 3 moles of tolylene diincyanate (TDI) were combined (co-adducted),
Made by Japan Polyurethane, NC0% 12.5, solid content 75%
) was stirred well at 50° C., and 880 parts of terminal amine propyl polydimethylsiloxane (molecular weight 2.200) having the following structure was gradually added dropwise thereto for reaction.

r11+ +13 (n is the molecular weight or a value of 2,200) After the reaction is complete, evaporate the ethyl acetate to form a transparent liquid intermediate 976.
part was obtained.

According to the infrared absorption spectrum of this intermediate, 2270/
The absorption due to free isocyanate groups in cm remains,
Moreover, an absorption band due to the 5i-0-C group was observed at 1090/cm.

Furthermore, when the amount of free incyanate groups in this intermediate was quantified, the theoretical value was 0.83%, whereas the actual value was 0.78%.

Therefore, the main structure of the above intermediate is estimated to be the following formula.

Reference Example 2 (Production Example of Intermediate) 24 parts of phenyl isocyanate was added to 196 parts of terminal hydroxypropylbolycymedylsiloxane (molecular weight 980) having the following structure, and the mixture was reacted with thorough stirring at 60°C to form a transparent liquid. 213 parts of reaction product were obtained.

(n is the value at which the molecular weight is 980) Next, a mixture of hexamethylene diisocyanate and water (Shuranate 24A-100, manufactured by Fukai Kasei, NC0% 23.5) 52
220 parts of the above reaction product were gradually added dropwise into the mixture at 60° C. with good stirring to react, yielding 263 parts of a colorless and transparent liquid intermediate.

According to the infrared absorption spectrum of this intermediate, 2270/
The absorption due to free isocyanate groups in cm remains,
Moreover, an absorption band due to the 5i-0-C group was observed at 10907 cm.

Furthermore, when the amount of free incyanate groups in this intermediate was quantified, the theoretical value was 1.54%, whereas the actual value was 1.37%.

Therefore, the main structure of the above intermediate is estimated to be the following formula.

Reference Example 3 (Production Example of Intermediate) 15 parts of n-butyraldehyde was added to 230 parts of terminal aminobutyl polysimethylsiloxane (molecular weight 1,150) having the following structure, and the reaction was carried out by stirring well at 80"C. The reaction was carried out for 3 hours while removing the produced water from the system under reduced pressure to obtain 238 parts of a transparent liquid reaction product.

(n is the molecular weight or a value of 1,150) Next, an adduct of 1 mol of trimethylolpropane and 3 mol of xylylene diisocyanate (Takenate DIION, manufactured by Takeda Pharmaceutical, NC 0% 115, solid content 75%) 186 While stirring well at room temperature, 490 parts of the above reaction product were gradually added dropwise to the mixture, and the mixture was reacted at 60°C.

After the reaction was completed, ethyl acetate was evaporated to obtain 610 parts of a transparent liquid intermediate.

According to the infrared absorption spectrum of this intermediate, 2270/
The absorption due to the free incyanate group of cm remains,
Moreover, an absorption band due to the 5i-0-C group was observed at 1090/cm.

Furthermore, when the amount of free incyanate groups in this intermediate was quantified, the theoretical value was 1.34%, whereas the actual value was 1.25%.

Therefore, the main structure of the above intermediate is estimated to be the following formula.

Reference Example 4 (Production Example of Intermediate) 35 parts of 2.6-dolylene cyanate and 110 parts of ethyl acetate were stirred well at 60°C, and a terminal mercaptopropyl polydimethylsiloxane (molecular weight 1.580) was gradually added dropwise to react.

0[S+ (CH3)201. S+ (CI+3)3(
(1, m, and n are values that give a molecular weight of 1,580) After the reaction was completed, ethyl acetate was evaporated to obtain 340 parts of a transparent liquid intermediate.

According to the infrared absorption spectrum of this intermediate, 2270/
The absorption due to free isocyanate groups in cm remains,
Moreover, an absorption band due to the 5i-0-C group was observed at 1090/cm.

Furthermore, when the amount of free incyanate groups in this intermediate was quantified, the theoretical value was 2.39%, whereas the actual value was 212%.

Therefore, the main structure of the intermediate represented by -1= is estimated to be the following formula.

(, 1, m, n are the values that give the molecular weight i, 580) Reference Example 5 (Production example of intermediate) 52 parts of hexamethylene diisocyanate and 1 part of ethyl acetate
While stirring well at 60° C., 450 parts of terminal hydroxypropylboridimethylsiloxane (molecular weight 2,250) having the structure shown below are gradually added dropwise to 60 parts to react.

(n is the value that gives a molecular weight of 1,580) After the reaction is complete, ethyl acetate is evaporated to form a transparent liquid intermediate 488
part was obtained.

According to the infrared absorption spectrum of this intermediate, 2270/
The absorption due to the free incyanate group of cm remains,
It showed an absorption band due to the 5i-0-C group at (''-) 1090/cm.

Furthermore, when the amount of free isocyanate groups in this intermediate was quantified, the theoretical value was 1.67%, whereas the actual value was 1.52%.

Therefore, the main structure of the above intermediate is estimated to be the following formula.

Reference Example 6 (Modification of resin) 150 parts of polybutylene adipate having a molecular weight of 2,000 and having a hydroxyl group at the end, 20 parts of 1,3-butylene glycol
and 52 parts of tolylene diisocyanate were subjected to an addition reaction in 412 parts of methyl ethyl ketone to give a viscosity of 200 poise/
A 20"C polyurethane resin solution (solid content 35%) was obtained.

5 parts of the intermediate of Reference Example 1 was added to 10 parts of this polyurethane solution, and the mixture was reacted at 80''C for 3 hours to obtain a modified resin solution (1) in which the intermediate and the polyurethane resin were combined.

In the modified resin obtained above, no incyanate group was observed by infrared absorption spectrum. This is presumed to be due to craft bonding of the intermediate to the resin.

Reference Example 7 (Modification of Resin) A modified resin solution (2) was obtained in the same manner as in Reference Example 6 except that the intermediate of Reference Example 2 was used in place of the intermediate in Reference Example 6.

In the modified resin obtained in Section 2, no incyanate group was observed by infrared absorption spectrum. This is presumed to be due to craft bonding of the intermediate to the resin.

Reference Example 8 (Resin Modification) Intermediate 3 of Reference Example 3 was added to 100 parts of a methyl ethyl ketone solution (solid content 30%) of a hinyl chloride/hinyl acetate/hinyl alcohol copolymer resin (S-LEC A, manufactured by Block Chemical).
The mixture was reacted at 80° C. for 3 hours to obtain a modified resin solution (3) in which the intermediate and vinyl resin were combined.

In the modified resin obtained above, no incyane-1 group was observed by infrared absorption spectrum. This is presumed to be an intermediate or a craft bond to the resin.

Reference Example 9 (Resin Modification) To 100 parts of a methyl ethyl ketone solution (solid content 30%) of polyvinyl butyral resin (S-LEC B, Sekisui Kajika), 3 parts of the intermediate from Reference Example 4 was added and reacted at 80°C for 3 hours. Then, a modified resin solution in which the intermediate and vinyl resin are combined (
4) was obtained.

In the modified resin obtained above, no incyanate group was observed by infrared absorption spectrum. This is presumed to be due to craft bonding of the intermediate to the resin.

Reference Example 10 (Modification of Resin) 5 parts of the intermediate of Reference Example 5 and 5 parts of vinyl acetate were added to an acrylic polyol (Hitaloid 3001, manufactured by 1 Ritsu Kasei Co., Ltd., solid content 50*) with good stirring, and reacted for 4 hours. A modified resin solution (5) in which the intermediate and the resin were combined was obtained.

In the modified resin obtained above, no incyanate group was observed by infrared absorption spectrum. This is presumed to be an intermediate or a graft bond to the resin.

Comparison reference example 1 Polyurethane resin solution on the modified side of Reference Example 6.

Comparison reference example 2
100 parts of polysiloxane resin (trade name, MS-841) manufactured by Shin-Etsu Chemical Co., Ltd. and the accompanying catalyst (
(trade name, PL-7) was dissolved in 1,000 parts of toluene to prepare a coating liquid for polysiloxane resin.

Examples 1 to 5 and Comparative Examples 1 to 2 The following release treatment agent was used at 100% modulus of 60 kg/c.
It was coated uniformly on one side of a 50 μm polyvinyl chloride film with a coating amount of 0.6 g solids/rnP, and dried by heating at 80° C. for 30 seconds to form a releasable coating layer. A sample was prepared with In addition, the temperature should be set to high temperature (100
When the temperature was lower than -1-), the polyvinyl chloride film softened and could not maintain its shape as a film.

An acrylic adhesive tape (manufactured by Mikki Kagaku) with a width of 20 mm (manufactured by Miki Kagaku Co., Ltd.) was pressed onto the coating Murakami thus prepared using a rubber roller weighing 2 kg. The peeling force, residual adhesive strength, residual adhesive strength retention rate, shedding property of the peelable coating layer, and writability with magic ink were measured after being left for 31 days at 90% or more, and the results are shown in Table 1 below. Ta.

Inutabi Example ↓ 100 parts of the resin solution of Reference Example 6 Coronate L (addition of trimethylolpropane and TDT)
2 parts methyl ethyl ketone
250 parts resin solution of reference example 7 according to disaster situation 100 parts coronate 2 parts fluororesin powder (Daikin T-Industry Nilbrone 1, -2)
5 parts methyl ethyl ketone 2
50 parts resin solution of Reference Example 8 100 parts coronate 2 parts methyl ethyl ketone
250 parts Example A 100 parts of the resin solution of Reference Example 9 Coronate 2 parts silicone resin powder (
Toshiba Silicone, Tospearl 120)
5 parts methyl ethyl ketone 25
0 Part Disaster Application 5 Reference Example 10 Resin solution 100 parts Coronat 2 parts Silicone resin powder (Toshiba Silicone, Tosvaal 120)
5 parts methyl ethyl ketone 2
50 parts resin solution of comparative reference example 10 100 parts silicone oil (Sl+-21) 0, east silicone)
5 parts methyl ethyl ketone
250 parts Mosquito box 100 parts Resin solution of Comparative Reference Example 2 Each evaluation was performed according to the following.

Peeling force: Attach an adhesive tape with a width of 20 mm to the releasable coating layer, store it at 40°C for 24 hours under a load of 20 g/C, and then peel it off by pulling it at a speed of 300 mm/min at an angle of 180°. The force (g) required for this was measured (20°C).

Residual Adhesion The adhesive tape after the peeling force measurement described above was attached to a #280 stainless steel plate, passed through a 2 kg de roller once and back, and after 30 minutes, pulled at a speed of 300 mm/min at an angle of 180° and peeled off. The force (g) required to do this was determined to be 4 (11 g) (at 20°C).

Residual adhesive strength retention rate: Shows the percentage of residual adhesive strength when a clean adhesive tape that has not been subjected to peel resistance is attached to stainless steel plate #280 and the adhesive strength to the stainless steel plate (320 g 720 m + n) is taken as 100%. .

Shedding property: 50 g/cm' for peelable coating layer
After the gauze is reciprocated once with a load of

Writability with marker ink: Characters were written on the releasable coating layer using a commercially available oil-based marker ink, and the presence or absence of ink repellency during writing was examined.

- row) □1-j arm 2 after 1G at room temperature (200C, 522) 32 25
+8 17 20 115 20*/la days later (
406C,90[)''2) :18 28
26 20 22 22 12 1 day after injury at room temperature (20'C, 5 days) 284
302 305 :llO:101 221
208ρ43 days later (40°C, 908JJI)
275 295 298 301 297
188 154 Remaining chestnut V Mushroom Salmon flavor ■ After room temperature 1B (20°C 52%) 88 94 9
5 96 94 69 55*ias (40”C,
90B, IJJ8692939492584B

Claims (4)

[Claims] (1) A releasable treatment agent characterized by containing a resin having a siloxane segment in its side chain. (2) The resin is polyurethane resin, polyurea resin,
The releasable treatment agent according to claim (1), which is selected from the group consisting of acrylic resins and vinyl resins. (3) Claim No. (1) further containing a releasable substance
) The releasable treatment agent described in item 2. (4) The stripping treatment agent according to claim (1), which is an organic solvent solution.