JP3372073B2 - UV curable transmissive screen resin composition and cured product thereof - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a video projector,
The present invention relates to an ultraviolet curable resin composition suitable for a transmissive screen such as a Fresnel lens or a lenticular lens used in a projection television or the like and a cured product thereof.

[0002]

2. Description of the Related Art Conventionally, a Fresnel lens is a thermoplastic resin,
For example, it was manufactured by a method of heating and pressurizing an acrylic resin or the like using a mold, and molding and molding, but this method has the following drawbacks. Since the mold is gradually cooled to prevent lens distortion, a process time of 30 to 60 minutes for one shot is required, resulting in extremely poor production efficiency. Since the mold is exposed to high temperature and high pressure, the mold is eroded, the prism shape of the Fresnel lens is changed, and the reproducibility of the Fresnel lens is deteriorated. Therefore, the life of the mold is short and the manufacturing cost is increased. In recent years, as a method that has high production efficiency and can be manufactured under mild conditions, a Fresnel lens mold is filled with an ultraviolet curable resin, and the surface is covered with a transparent plastic film. It has become possible to manufacture a Fresnel lens comprising a transparent plastic film and an ultraviolet curable resin layer laminated on the transparent plastic film by irradiating the resin with the resin.

[0003]

However, this method has the following problems. The ultraviolet-cured product is poorly released from the mold and cannot be released, or the resin remains in the mold at the time of release and the mold cannot be used.

[0004]

Means for Solving the Problems As a result of intensive studies, the inventors of the present invention have shown that the mold releasing property from the mold is excellent, the surface is excellent in scratch resistance and the shape is maintained at a long-term use temperature (60 ° C.). It has been found that it is possible to manufacture an inexpensive Fresnel lens having high productivity and excellent adhesion to a transparent film, and having high production efficiency, and completed the present invention.

That is, the present invention relates to the polyol compound (a)
And urethane (meth) acrylate (A), which is a reaction product of the organic polyisocyanate (b) and the compound (c) represented by the formula (1),

[0006]

[Chemical 3]

(Wherein R ₁ is a hydrogen atom or a methyl group, R 1
₂ is a C ₁ -C ₅ alkyl group,

[0008]

[Chemical 4]

Alternatively, R ₆ --OCH _2- , R ₃ , R ₄ , R
₅ are each independently a hydrogen atom, a phenyl group, C ₁ -C
_{5 is} an alkyl group or a bromine atom, R ₆ is a C _{1 to} C ₁₀ alkyl group, and n is a number of 1 to 5. The present invention relates to a resin composition for a UV-curable transmissive screen, which contains a reactive diluent (B) and a photopolymerization initiator (C), and a cured product thereof.

The urethane (meth) acrylate (A) used in the present invention can be obtained by reacting the polyol compound (a) with the organic polyisocyanate (b) and the compound (c) represented by the formula (1). it can. Specific examples of the polyol compound (a), which is a raw material of the urethane (meth) acrylate (A), include ethylene glycol,
Neopentyl glycol, 1,4-butanediol,
Polyalkylene polyols such as alkylene glycols such as 1,6-hexanediol and 3-methyl-1,5-pentanediol, polyethylene glycol, polytetramethylene glycol, bisphenol A polyethoxydiol, bisphenol F polyethoxydiol; succinic acid, Polyester polyol obtained by reaction of dibasic acid such as adipic acid, azelaic acid, sebacic acid, phthalic acid, tetrahydrophthalic acid or the anhydride thereof with the alkylene glycol or the polyether polyol; poly ε-caprolactone modified polyol; polycarbonate A polyol etc. can be mentioned.

Specific examples of the organic polyisocyanate (b) include tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and trimethylhexamethylene diisocyanate.

Specific examples of the compound (c) represented by the above formula (1) include 2-hydroxypropyl (meth).
Acrylate, 2-hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenyloxy-propyl (meth) acrylate, 2-hydroxy-3- (2'-
Phenylbenzene) oxy-propyl (meth) acrylate, 2-hydroxy-3- (4'-phenylbenzene) oxy-propyl (meth) acrylate, 2-hydroxy-3- (2 ', 4', 6'-tribromo Phenyl) oxy-propyl (meth) acrylate, 2-hydroxy-3- (2 ', 4'-dibromophenyl) oxy-propyl (meth) acrylate, 2-hydroxy-3
-Pentyloxy-propyl (meth) acrylate, 2
-Hydroxy-3-hexyloxy-propyl (meth)
An acrylate etc. can be mentioned.

The urethane (meth) acrylate (A)
Is, for example, an isocyanate group of the organic polyisocyanate (b) is preferably 1.1 to 2.0 equivalents per 1 equivalent of the hydroxyl group of the polyol compound (a), and the reaction temperature is preferably 70.
To 90 ° C. to synthesize a urethane oligomer, and then a hydroxyl group of the compound (c) represented by the above formula (1), preferably 1 to 1.5 equivalents, is preferably used at a reaction temperature per 1 equivalent of the isocyanate group of the urethane oligomer. Is 70-90
It can be obtained by reacting at ° C. Preferred urethane (meth) acrylates include polyester urethane acrylate, polycaprolactone urethane acrylate, and polytetramethylene urethane acrylate.

The urethane (meth) acrylate (A) is contained in the resin composition in an amount of preferably 10 to 60% by weight, particularly preferably 15 to 55% by weight. Next, specific examples of the reactive diluent (B) used in the present invention include, for example, phenyloxyethyl (meth) acrylate, nonylphenyloxyethyl (meth) acrylate, phenylpolyethoxy (meth) acrylate, o-phenyl. (Meth) acrylate of ethylene oxide adduct of phenol, acryloylmorpholine, N-vinylcaprolactam, 2
-Hydroxypropyl (meth) acrylate, 2-hydroxypropyl-3-oxyphenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, ε-
Caprolactone modified hydroxypivalic acid neopentyl glycol di (meth) acrylate, bisphenol A
Examples thereof include polyethoxydi (meth) acrylate, bisphenol F polyethoxydi (meth) acrylate, nonanediol di (meth) acrylate and polyethylene glycol di (meth) acrylate. The reactive diluent (B) is contained in the resin composition in an amount of preferably 35 to 85% by weight, particularly preferably 40 to 80% by weight.

In the present invention, as the reactive compound other than the components (A) and (B), for example, 2,4,6-tribromophenyloxyethyl (meth) acrylate, 2,4,6-
Tribromophenyloxypropyl (meth) acrylate, 2,4,6-tribromophenyl (meth) acrylate, tetrabromobisphenol A polyethoxydi (meth) acrylate, bisphenol A type epoxy (meth) acrylate, bisphenol F type epoxy (meth) Acrylate or the like can be used.

Examples of the photopolymerization initiator (C) used in the present invention include 1-hydroxycyclohexyl phenyl ketone, acetophenone dimethyl ketal, 2-hydroxy-2-methyl-1-phenylpropan-1-one and the like. be able to. The content of the photopolymerization initiator (C) in the resin composition is preferably 0.1 to 15% by weight, particularly preferably 0.5 to 5% by weight.

The resin composition of the present invention can be obtained by a method of heating, dissolving and mixing the components (A), (B) and (C). The refractive index (23 ° C.) of the resin composition of the present invention is 1.
It is preferably 53 or more.

In the resin composition of the present invention, if necessary,
A release agent, a defoaming agent, a leveling agent, an antistatic agent, a light stabilizer, an antioxidant, a polymerization inhibitor and the like can be used.

The cured product of the resin composition of the present invention can be obtained by irradiating the resin composition with ultraviolet rays according to a conventional method. Specifically, the resin composition of the present invention, for example,
It is applied on a stamper having the shape of a Fresnel lens or a lenticular lens, a layer of the resin composition is provided, and a hard transparent substrate (for example, polyvinyl chloride, polystyrene, polycarbonate, poly (meth) acrylate, polyester is provided on the layer. Alternatively, a transparent substrate or the like made of a blended product of these polymers is adhered, and then the resin composition is cured by irradiating ultraviolet rays from the hard transparent substrate side with a high pressure mercury lamp or a metal halide lamp in that state. , Peeling from the stamper. In this way, the ordinary refractive index (23 ° C.) is 1.55 or more, and 1.
A transmission screen such as a soft Fresnel lens or a lenticular lens having 56 or more can be obtained.

[0020]

EXAMPLES Next, the present invention will be described more specifically with reference to Examples and Comparative Examples.

Synthetic Example of Urethane (Meth) Acrylate (A) Synthetic Example 1 4 mol ethylene oxide adduct of bisphenol F 3
76 parts, tolylene diisocyanate 348 parts were charged,
After heating, the mixture was reacted at 80 ° C. for 10 hours, and then 2-hydroxy-3-phenyloxy-propyl acrylate 46.
6.2 parts, metoquinone 0.6 part, dilauric acid di-n-
0.35 parts of butyltin was charged and the reaction was carried out at 80 ° C. The refractive index (25 ° C.) of the obtained urethane acrylate (A-1) was 1.570.

Synthesis Example 2 Polyester diol consisting of 3-methyl-1,5-pentadiol and terephthalic acid (OH value 112.2 mg KO
H / g, molecular weight 1000) 1000 parts, hexamethylesiisocyanate 336 parts were charged and reacted at 80 ° C. for 10 hours after heating, and then 2-hydroxy-3-phenyloxy-propyl acrylate 466.2 parts and metquinone 0.9. And 0.5 part of di-n-butyltin dilaurate were charged and the reaction was carried out at 80 ° C. The refractive index (25 ° C.) of the obtained urethane acrylate (A-2) was 1.531.
Met.

Synthesis Example 3 668 parts of an ethylene oxide 10 mol adduct of bisphenol A and 348 parts of tolylene diisocyanate were charged and reacted at 80 ° C. for 10 hours, then 300 parts of 2-hydroxybutyl acrylate and 0.66 part of metoquinone dilauric acid. Charge 0.4 parts of di-n-butyltin, 80
The reaction was carried out at ° C. Obtained urethane acrylate (A
The refractive index (25 ° C) of -3) was 1.548.

Examples of Resin Composition Examples 1 to 4 and Comparative Examples 1 and 2 UV curable transmissive screen resins prepared by mixing the components shown in Table 1 (numerical values indicate parts by weight) with each component. A composition was obtained. Table 2 shows the characteristics and cured physical properties of Fresnel lenses obtained from these resin compositions. The performance evaluation of the Fresnel lens was performed with the Fresnel lens obtained by the following manufacturing method. Manufacturing method of Fresnel lens The resin composition of each Example and Comparative Example heated at 50 ° C. is formed into a nickel mold in which prisms having a height of 200 μm and a width of 80 μm are concentrically carved, and a thickness of 300 μm. And then coated with a 1.5 mm polycarbonate sheet. Next, the polycarbonate sheet was irradiated with ultraviolet rays at 1000 mJ / cm ² from a high-pressure mercury lamp to cure it, and then it was released from the mold and an ultraviolet-curable resin layer was laminated on the polycarbonate sheet to obtain a Fresnel lens.

The performance of the Fresnel lens manufactured as described above was evaluated by the following method. (1) Releasability: Difficulty in releasing the cured resin from the mold ○ ・ ・ ・ ・ Releasability from the mold is good △ ・ ・ ・ ・ Releasing is somewhat difficult × ・ ・ ・The mold is difficult or the mold is dull (2) Mold reproducibility: The surface shape of the cured resin layer and the surface shape of the mold were observed. ○ ・ ・ ・ ・ Reproducibility is good × ・ ・ ・ ・ Reproducibility is poor

(3) Restorability: After a metal round bar having a diameter of 10 mm was strongly pressed against a Fresnel lens manufactured using a resin composition, the time until the trace of the round bar on the lens completely disappeared was measured. . ◎ ・ ・ ・ ・ It disappears instantly ○ ・ ・ ・ ・ ・ ・ Disappeared within 60 seconds △ ・ ・ ・ ・ Disappeared between 60 seconds and 60 minutes × ・ ・ ・ ・ ・ ・ Not disappeared

(4) Scratch resistance: A Fresnel lens manufactured by using a resin composition and an acrylic plate (width 15 mm, length 1)
(00 mm, thickness 2 mm) is strongly pressed vertically, and the space having a length of 100 mm is reciprocated 10 times at a speed of 1 reciprocation of 1 second, and then scratches are observed on the lens surface. ◎ ・ ・ ・ No scratches are observed ○ ・ ・ ・ ・ Striped scratches are recognized △ ・ ・ ・ ・ Strip-shaped scratches are partially observed × ・ ・ ・ ・ ・ ・ Strip-shaped scratches on the entire surface Is recognized

(5) Adhesion: A resin composition is coated on a hard transparent substrate (width 20 mm, length 150 mm, film thickness 2)
(00 μm), and then 500 mJ / cm ^{2 was} irradiated with a high pressure mercury lamp (80 W / cm, ozoneless) for curing. Then, the 90-degree peel strength of the resin cured on the hard transparent substrate was measured with a tensile tester. (Peeling speed, 100 mm / min) ◎ ・ ・ ・ ・ Peeling strength 2 kg / cm or more ○ ・ ・ ・ ・ Peeling strength 1-2 kg / cm △ ・ ・ ・ ・ Peeling strength 0.5 -1 kg / cm × ・ ・ ・ ・ Peeling strength 0.5 kg / cm or less (6) Refractive index (23 ° C): The refractive index (23 ° C) of the resin composition and its cured product was measured.

[0029]

[Table 1]                                   Table 1                                 Actual Example Comparative Example                             1 2 3 4 1 2 (A) component Urethane acrylate (A-1) 40 Urethane acrylate (A-2) 39.1 15 Urethane acrylate (A-3) 33 15 Urethane acrylate * 1 40 33 (B) component KAYARAD R-551 * 2 9.8 Neomar BA-801 * 3 10 19.6 33 40 10 33 KAYARAD OPP-2 * 4 30 29.4 15 30 N-vinyl caprolactam 5 5 5 5 5 KAYARAD R-128 * 5 0.98 13 10 13 (C) component Irgacure 184 * 6 0.98 3 3 0.98 3 Other ingredients 2,4,6-tribromophenyl 15 18 15 18 Oxyethyl acrylate

Note * 1 Urethane acrylate: Ethylene oxide 10 mol adduct of bisphenol A 6
Charge 68 parts, 348 parts of tolylene diisocyanate,
After reacting at 80 ° C. for 10 hours, 243.6 parts of 2-hydroxyethyl acrylate, 0.6 part of methoquinone and 0.38 part of di-n-butyltin dilaurate were charged, and 80
Reaction was carried out at ° C to obtain urethane acrylate. * 2 KAYARAD R-551: Nippon Kayaku Co., Ltd.
Bisphenol A poly (n = 4) ethoxydiacrylate * 3 Neomer BA-801: Sanyo Kasei Co., Ltd. bisphenol A poly (n = 8) ethoxydiacrylate * 4 KAYARAD OPP-2: Nippon Kayaku Co., Ltd. )
O-phenylphenol poly (n = 2) ethoxy acrylate * 5 KAYARAD R-128 manufactured by Nippon Kayaku Co., Ltd.
2-hydroxypropyl-3-oxyphenyl acrylate * 6 Irgacure 184: Ciba Geigy,
Photopolymerization initiator 1-hydroxycyclohexyl phenyl ketone

[0031]

[Table 2]                                   Table 2                                 Actual Example Comparative Example                           1 2 3 4 1 2 Refractive index of liquid (23 ℃) 1.551 1.532 1.535 1.531 1.543 1.537 Releasability ○ ○ ○ ○ × △ Mold reproducibility ○ ○ ○ ○ ○ ○ Restorability ◎ ◎ ◎ ◎ ◎ ◎ ◎ Scratch resistance ◎ ◎ ◎ ◎ ◎ ◎ ◎ Adhesion ◎ ○ ◎ ◎ ◎ ◎ Refractive index of cured product (23 ℃) 1.571 1.552 1.555 1.551 1.563 1.557

From Table 2, the resin composition of the present invention and the cured product thereof are excellent in mold releasability, mold reproducibility, scratch resistance, adhesion, restoration property and the like.

[0033]

The cured product of the resin composition of the present invention is excellent in releasability and is particularly suitable for a transmission screen.

─────────────────────────────────────────────────── ─── Continuation of the front page (56) Reference JP-A-5-155944 (JP, A) JP-A-5-247156 (JP, A) JP-A-5-255464 (JP, A) JP-A-5- 255463 (JP, A) JP 5-287039 (JP, A) JP 5-78507 (JP, A) JP 5-320286 (JP, A) JP 4-288314 (JP, A) JP-A-3-200949 (JP, A) JP-A-3-157412 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08F 290/06 G03B 21/62 C08G 18/67

Claims (2)

(57) [Claims] 1. A urethane (meth) acrylate (A) which is a reaction product of a polyol compound (a), an organic polyisocyanate (b) and a compound (c) represented by the formula (1), (In the formula, R ₁ is a hydrogen atom or a methyl group, and R ₂ is C ₁ to C.
An alkyl group of ₅ , embedded image Alternatively, R ₆ —OCH ₂ —, R ₃ , R ₄ , and R ₅ are each independently a hydrogen atom, a phenyl group, a C _{1 to} C ₅ alkyl group or a bromine atom, and R ₆ is a C _{1 to} C _{10 group} . Alkyl group, n
Is a number from 1 to 5. ) A resin composition for a UV-curable transmissive screen, which contains a reactive diluent (B) and a photopolymerization initiator (C). 2. A method for producing a cured product, which comprises irradiating the resin composition according to claim 1 with ultraviolet rays.