JP5206464B2 - Compound having perfluoropolyether group, urethane group and (meth) acryloyl group - Google Patents

Description

  The present invention relates to a compound having a perfluoropolyether group, a urethane group and a (meth) acryloyl group.

  In recent years, plastics (polycarbonate, polymethyl methacrylate, polystyrene, polyester, polyolefin, epoxy resin, melamine resin, triacetyl cellulose resin, ABS resin, AS resin, norbornene resin, etc.), metal, wood, paper, glass, slate, etc. As a protective coating material and anti-reflection coating material for preventing scratches (abrasion) on various substrate surfaces and preventing contamination, it has excellent coating properties, and the surface of each substrate has hardness, Curing composition capable of forming a cured film excellent in any of scratch resistance, antifouling property, abrasion resistance, surface slipperiness, low curling property, adhesion, transparency, chemical resistance and appearance of coating surface Things are requested.

In order to satisfy such a request, various compositions have been proposed, but have excellent coating properties as a curable composition, and when it is a cured film, has high hardness and scratch resistance, At present, no product with the characteristics of excellent transparency and antifouling properties has been obtained.
As a method for imparting antifouling properties, for example, Patent Document 1 describes a curable composition containing a polysiloxane having a (meth) acryloyl group. However, there is room for further improvement from the viewpoint of oil marker wiping. was there.

  Patent Document 2 discloses a composition for forming an antireflection film that can improve the slipperiness of the surface of the antireflection film, is soluble in a non-fluorine general-purpose solvent, and is easy to form a thin film. This composition for forming an antireflection film is a composition comprising a reactive surface modifier (I) and an antireflection film material (II), of which the reactive surface modifier (I) is (A A reactive group-containing composition comprising a reaction product of a triisocyanate trimerized from a diisocyanate and (B) at least two active hydrogen-containing compounds, wherein the component (B) is (B-1) The composition comprises a perfluoropolyether having at least one active hydrogen and (B-2) a monomer having an active hydrogen and a self-crosslinkable functional group. By adding such a reactive surface modifier (I), the surface properties of the antireflection film, especially surface slipperiness (lower coefficient of friction), surface hardness, wear resistance, chemical resistance, contamination wiping It is described that the surface property improved by improving the property, water repellency, oil repellency, solvent resistance, etc. can be imparted to the surface of the original coating film. The antireflection film material (II) combined with the reactive surface modifier (I) is for forming a low refractive index layer.

JP-A-2005-36018 JP 2006-37024 A

  The present invention has been made in view of the above-mentioned problems, and urethane (meta) containing a perfluoropolyether group capable of imparting excellent transparency and antifouling properties, particularly oily marker wiping properties, to the resulting cured film. ) To provide acrylates.

［式中、Ｒ^１は水素原子又はメチル基であり、Ｒ^３は単結合、メチレン基又はエチレン基であり、Ｒ^４及びＲ^５はそれぞれ独立にフッ化メチレン基又は炭素数２〜４のパーフルオロアルキレン基であり、ｎは５〜５０の整数である。］
５．前記Ｒ^１が水素原子である上記４に記載の化合物。
６．前記ｎが１０〜３０の整数である上記４又は５に記載の化合物。
７．（Ａ）パーフルオロポリエーテル構造を有するジオール化合物と、芳香族ジイソシアネート化合物とを反応させる工程、
（Ｂ）水酸基及び５個以上の（メタ）アクリロイル基を有する化合物を反応させる工程
を含む、上記１に記載の化合物の製造方法。 That is, this invention provides the following compound and its manufacturing method.
1. Perfluoropolyether group, urethane group obtained by reacting a reaction product of a diol compound having a perfluoropolyether structure with an aromatic diisocyanate compound with a compound having a hydroxyl group and 5 or more (meth) acryloyl groups. And a compound having 10 or more (meth) acryloyl groups.
2. 2. The compound according to 1 above, wherein the aromatic diisocyanate is 2,4-tolylene diisocyanate.
3. 3. The compound according to 1 or 2 above, wherein the compound having 5 or more (meth) acryloyl groups is dipentaerythritol penta (meth) acrylate.
4). The compound in any one of said 1-3 shown by following General formula (1).

[Wherein, R ¹ is a hydrogen atom or a methyl group, R ³ is a single bond, a methylene group or an ethylene group, and R ⁴ and R ⁵ are each independently a methylene fluoride group or a C 2-4 par. A fluoroalkylene group, n is an integer of 5 to 50; ]
5. 5. The compound according to 4 above, wherein R ¹ is a hydrogen atom.
6). 6. The compound according to 4 or 5 above, wherein n is an integer of 10 to 30.
7). (A) a step of reacting a diol compound having a perfluoropolyether structure with an aromatic diisocyanate compound,
(B) The manufacturing method of the compound of said 1 including the process with which the compound which has a hydroxyl group and five or more (meth) acryloyl groups is made to react.

  When added to the curable composition, the compound of the present invention can impart excellent transparency and antifouling property, particularly oily marker wiping properties, to the resulting cured film.

2 is an IR chart of Compound 1. 1 is a ¹ H NMR chart of Compound 1. 2 is a ¹³ C { ¹ H} NMR chart of ¹³ C { ¹ H} of Compound 1. FIG.

Hereinafter, the compound of the present invention will be specifically described.
The compound of the present invention is a perfluoropolyether group obtained by adding a compound having 5 or more (meth) acryloyl groups to the reaction product of a diol compound having a perfluoropolyether structure and an aromatic diisocyanate. And having a urethane group and 10 or more (meth) acryloyl groups.

  As aromatic diisocyanates, metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4-naphthalene diisocyanate 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, 2,7-naphthalene diisocyanate, etc. are mentioned, and metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, preferable.

  Examples of the compound having 5 or more (meth) acryloyl groups include dipentaerythritol penta (meth) acrylate and tripentaerythritol hexa (meth) acrylate, and dipentaerythritol penta (meth) acrylate is preferable.

Furthermore, the compound of the present invention preferably has a structure represented by the following general formula (1).

In formula (1), R ¹ is a hydrogen atom or a methyl group, and is preferably a hydrogen atom.
R ³ is a single bond, a methylene group or an ethylene group.
R ⁴ and R ⁵ each independently represent a methylene fluoride group (—CF ₂ —) or a C 2-4 perfluoroalkylene group, and are a methylene fluoride group, a perfluoroethylene group, or a perfluoropropylene group. Is preferred.
n is an integer of 5 to 50, preferably an integer of 10 to 30. When n is smaller than 5, there is a possibility that sufficient slipping property and oil marker wiping property may not be obtained when formed into a coating film, and when it is larger than 50, solubility in a solvent may be impaired.

  The molecular weight of the compound of the present invention is usually in the range of 2000 to 6000, preferably in the range of 2500 to 3500. Here, the molecular weight is measured by gel permeation chromatography.

The compound of the present invention can be produced by the following production method of the present invention.
The production method of the present invention comprises (A) a step of reacting a diol compound having a perfluoropolyether structure with an aromatic diisocyanate compound,
(B) It includes a step of reacting a compound having a hydroxyl group and 5 or more (meth) acryloyl groups.

  More specifically, the perfluoropolyether compound having a hydroxyl group is mixed with a diisocyanate compound in a solvent such as methyl ethyl ketone or without solvent, and cooled in a 10-20 ° C. water bath. When the temperature of the solution reaches 10 to 20 ° C, a Lewis acid catalyst such as dibutyltin dilaurate is added, and the reaction solution is stirred in the range of 20 to 65 ° C for 1 to 3 hours. It can manufacture by mixing the compound which has 5 or more (meth) acryloyl groups and a hydroxyl group after that, and stirring for 3 to 6 hours at 45-65 degreeC.

The diol compound having a perfluoropolyether structure is not particularly limited as long as it is a compound having hydroxyl groups at both ends of the perfluoropolyalkylene oxide, but the terminal diol compound of perfluoropolyethylene oxide, the terminal diol compound of perfluoropolypropylene oxide Is preferred.
Examples of commercially available diol compounds having a preferred perfluoropolyether structure include Fluorolink D10H, Fluorolink D (manufactured by Solvay Solexis) and the like.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. Unless otherwise specified, “%” represents mass%, and “part” represents mass part.

［上記式中、ｎ＝１０〜１５である。］ Example 1
Synthesis of compound 1

[In the above formula, n = 10-15. ]

  In a reaction vessel equipped with a stirrer, a reflux pipe and a dry air introduction pipe, 2,6-di-t-butyl-p-cresol (Yoshinox BHT, manufactured by Yoshitomi Fine Chemical Co., Ltd.) (0.024 g, 0.1 mmol), Fluoropolyetherdiol (manufactured by Solvay Solexis, Fluorolink D10H) (37.00 g, 24.6 mmol), 2,4-tolylene diisocyanate (manufactured by Mitsui Chemicals Polyurethane Co., Ltd., TOLDY-100) (8.58 g, 49.2 mmol) ) And methyl ethyl ketone (manufactured by Maruzen Petrochemical Co., Ltd.) (45.58 g) are added and cooled in a water bath. After adding dibutyltin dilaurate (manufactured by Kyodo Yakuhin Co., Ltd., CASTIN-D) (0.080 g, 0.1 mmol) at 10 ° C. ± 5 ° C., the temperature was raised to 60 ° C. and heated for 1.5 hours. Next, the reaction mixture was cooled in a water bath, and dipentaerythritol pentaacrylate (Atotonix M403, manufactured by Toagosei Co., Ltd.) (108.84 g) diluted with methyl ethyl ketone to a solid content concentration of 50% was added thereto using a dropping funnel. Added. This was heated to 60 ° C. and heated for 4 hours. Thus, a methyl ethyl ketone solution (200 g) of Compound 1 represented by the above chemical structural formula was obtained.

The IR chart, ¹ H NMR chart, and ¹³ C { ¹ H} NMR chart of the obtained compound 1 are shown in FIGS.

<Manufacture of curable composition>
Example 2
Silica particle dispersion (dispersion medium: methyl ethyl ketone, manufactured by Nissan Chemical Co., Ltd .: product name MEK-ST-L) 216.9 parts by mass (65.08 parts by mass as silica particles) was concentrated to a solid content of 70%, 31.62 parts by mass of dipentaerythritol hexaacrylate (manufactured by Nippon Kayaku Co., Ltd .: KAYARAD DPHA), 3.00 parts by mass of photoinitiator (manufactured by Ciba Specialty Chemicals: Irgacure 184), 70 parts by mass of methyl isobutyl ketone After mixing, 0.3 part by mass of Compound 1 synthesized in Example 1 was added and stirred. Furthermore, methyl ethyl ketone was added so that the solid content concentration was 50% by mass and stirred to obtain a curable composition.

Comparative Example 1
A curable composition was obtained in the same manner as in Example 2 except that each component was blended in the amounts shown in Table 1.

<Manufacture of cured film>
Each curable composition obtained in Example 2 and Comparative Example 1 was coated on a TAC film having a thickness of 80 μm using a bar coater (12 mil). After drying at 80 ° C. for 2 minutes, each cured film was prepared by irradiating with ultraviolet rays at an intensity of irradiation of 1.0 J / cm ² under air using a high pressure mercury lamp and photocuring.

<Evaluation of physical properties of cured film>
The haze, total light transmittance, and contact angle of the obtained cured film were measured. Moreover, oil-based marker wiping property, steel wool resistance, and coating film appearance were evaluated. The results are shown in Table 1.

(1) Measurement of haze (%) The haze (%) of the cured film was measured using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.) in accordance with JIS K7105.

(2) Measurement of total light transmittance (Tt;%) The total light transmittance (%) of the cured film was measured according to JIS K7105 using a color haze meter (manufactured by Suga Test Instruments Co., Ltd.). .

(3) Oil marker wiping test An oil marker (Zebra Co., Ltd., McKee MO-120-MC-BK) was attached to the cured film, and after 30 seconds, wiped with a non-woven fabric (Asahi Kasei brand name: Bencott S-2). It was. When it was completely wiped off, an oily marker was attached again, and wiping was repeated again. The number of possible wipings was counted and evaluated according to the following evaluation criteria.
A: Oil marker wiping possible 10 times or more B: Oil marker wiping possible 5-10 times C: Oil marker wiping possible 1 to 4 times D: Oil marker wiping possible 0 times

(4) Measurement of contact angle (°) The contact angle of the cured film with respect to water and hexadecane was measured according to JIS 6768 using a contact angle meter Drop Master 500 manufactured by Kyowa Interface Chemical Co., Ltd.

  From the results in Table 1, it can be seen that the cured film obtained by curing the curable composition to which the compound of the present invention is added is excellent in transparency and oil-based marker wiping property. It can also be seen that both water and hexadecane have high contact angles and are excellent in water resistance and oil resistance.

The compound of the present invention can impart excellent transparency and antifouling property to a cured film obtained by curing the curable composition by adding it to the curable composition. Useful as an agent.
In particular, since the transparency of the cured film is not impaired, it is useful as an additive for a cured film for optical applications.

Claims (8)

  Perfluoropolyether group, urethane group obtained by reacting a reaction product of a diol compound having a perfluoropolyether structure with an aromatic diisocyanate compound with a compound having a hydroxyl group and 5 or more (meth) acryloyl groups. And a compound having 10 or more (meth) acryloyl groups.   The aromatic diisocyanate is metaphenylene diisocyanate, paraphenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, dimethylbenzene diisocyanate, ethylbenzene diisocyanate, isopropylbenzene diisocyanate, tolidine diisocyanate, 1,4-naphthalene diisocyanate. The compound according to claim 1, which is 1,5-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, or 2,7-naphthalene diisocyanate.   The compound according to claim 1 or 2, wherein the aromatic diisocyanate is 2,4-tolylene diisocyanate.   The compound according to any one of claims 1 to 3, wherein the compound having 5 or more (meth) acryloyl groups is dipentaerythritol penta (meth) acrylate. The compound of any one of Claims 1-4 shown by following General formula (1).

[Wherein, R ¹ is a hydrogen atom or a methyl group, R ³ is a single bond, a methylene group or an ethylene group, and R ⁴ and R ⁵ are each independently a methylene fluoride group or a C 2-4 par. A fluoroalkylene group, n is an integer of 5 to 50; ] The compound according to claim 5, wherein R ¹ is a hydrogen atom.   The compound according to claim 5 or 6, wherein n is an integer of 10 to 30. (A) a step of reacting a diol compound having a perfluoropolyether structure with an aromatic diisocyanate compound,
(B) The manufacturing method of the compound of Claim 1 including the process with which the compound which has a hydroxyl group and five or more (meth) acryloyl groups is made to react.

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