JPH05132557A - New modified polysiloxane compound and radiation-curable composition containing the same - Google Patents

Abstract

PURPOSE:To prepare the subject compsn. capable of forming a film which retains excellent clarity, water repellency, and hardness for a long time and is useful for forming a hard coating film of an optical disc by incorporating a specific modified polysiloxane compd. into the compsn. CONSTITUTION:A modified polysiloxane compd. of the formula [wherein R1 and R2 are each H or CH3; 0<=x<=200; 4<=y<=30; 1<=z<=40; (y+z)/x>=0.25; and 5<=j<=20] is incorporated into a compsn. The compd. is useful as a modifier or surface protective agent for a molded plastic article and is esp. suitable as an additive for an ultraviolet-curable resin for forming a hard coating film of an optical disc. An ultraviolet-curable compsn. [mainly comprising a monomer having at least three (meth)acryloyl groups] contg. the compd. forms a coating film retaining excellent clarity, water repellency, and hardness for a long time.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The modified polysiloxane compound of the present invention can be used for modifying plastic moldings and as a surface protective material for plastic moldings. In particular, it is an ultraviolet curable resin used for hard coating films of optical disks. Can be suitably used as an additive to Hereinafter, the present invention will be described by taking as an example the case where it is applied to a hard coating film of an optical disc.

[0002]

2. Description of the Related Art For example, a radiation-curable composition, particularly an ultraviolet-curable composition used for a protective film (hard coating film) of an optical disk generally gives a high crosslinking density as a main material in order to impart high hardness. A polyfunctional monomer such as trimethylolpropane triacrylate and pentaerythritol tri / tetraacrylate is used, and various additives are added thereto.

As various additives, prepolymers such as polyester acrylates, polyether acrylates and urethane acrylates for obtaining flexibility and adhesiveness, and reactivity for viscosity adjustment during coating film formation. As a diluent, a monoacrylate such as 2-ethylhexyl acrylate, cyclohexyl acrylate or hydroxyethyl acrylate, or a diacrylate such as 1,6-hexanediol diacrylate and tripropylene glycol diacrylate or polyethylene glycol diacrylate, and further photopolymerization initiation Agents and polymerization accelerators.

This composition is applied to a substrate such as plastic,
By a coating method such as roll coating, gravure coating, and spin coating, it is applied to have a thickness of several microns and is cured by irradiation with radiation such as ultraviolet rays and electron beams. Needless to say, it is not necessary to add a photopolymerization initiator when curing with an electron beam.

Although the above composition is a solvent-free composition, it is diluted with a solvent such as toluene or alcohol,
There may be a case where the coating is dried and then radiation-cured.

[0006]

Since the hard coating film of the optical disk thus manufactured has a high hardness, it has an advantage that it is not easily scratched, but has the following problems. That is, since the composition forming the hard coating film contains many functional groups such as ester groups and hydroxyl groups that easily attract moisture, the water repellency is insufficient, and especially in a high humidity environment, the hard coating film Since water is adsorbed on the surface of the optical disk, dust and dirt are easily attached to the surface of the optical disk, and the optical disk is easily soiled.

Further, since the hard coating film has a large electric resistance in a relatively low humidity environment, it is easily charged by friction and contact, and thus attracts dust and dirt, impairing the appearance of the optical disk. .. Furthermore, this static electricity deteriorates various performances. Therefore, in order to supplement this, various antistatic agents are added to the composition for the hard coating film, or a large amount of reactive surfactants are mixed for antistatic and immobilized by copolymerization. Attempts have also been made to impart antistatic performance.

However, in the method utilizing bleed-out by adding an antistatic agent, since the composition has a high crosslinking density, the glass transition point of the hard coating film is high and a sufficient antistatic effect is obtained. Can't get, and also
Even if the antistatic agent bleeds out on the surface of the film, it is not fixed, so it is difficult to maintain its effect over a long period of time, and a method of adding the antistatic agent is also preferable. In any of the methods of immobilizing by copolymerization, even if the antistatic effect is obtained, the surfactant adsorbs water on the surface of the coating film to prevent electrification. On the surface of the hard coating film, the concentration of dust and dirt becomes high, and it becomes easy to get dirty.

In order to impart water repellency, generally, a method of adding and mixing a polydimethylsiloxane or a fluorine-based material to a coating material and curing the coating material can be considered. However, a commercially available polydimethylsiloxane or a fluorine-based material is used. When added to and mixed with the (meth) acrylic material, which is the main material of the composition for hard coating film of optical disk, it is incompatible in most cases and phase separation occurs, so that it cannot be applied uniformly. As a result, the coating film after curing becomes opaque and becomes fatal.

There is also a method of coating the surface of the hard coating film without adding polydimethylsiloxane or a fluorine-based material, but in order to maintain high hardness and maintain water repellency for a long period of time. The surface coating method is disadvantageous in terms of adhesion and the like. Further, as a compound used for imparting water repellency, (meth) acryloyl-modified polydimethylsiloxane has conventionally been present, but most of them are (meth) at one end or both ends of a chain polydimethylsiloxane skeleton. Since it has a structure with an acryloyl group, it is generally used for copolymerization with a radical-polymerizable monomer or for graft polymerization on a base active group.

As an example involving a photocuring reaction, a compound having a low acryloyl concentration, which has a (meth) acryloyl group at one or both ends of a long chain dimethylsiloxane unit as described above, is prepared by using an adhesive tape or the like. An example of using it as a part of the peeling raw material is mentioned. On the other hand, there are also compounds having a (meth) acryloyl group in the side chain, but the definition of the structure is ambiguous, and in particular, the compatibility with a monomer having three or more (meth) acryloyl groups is poor and the properties after coating and curing are high. Has water repellency but becomes opaque, and cannot be used as a hard coating film for an optical disc, for example.

There are also polyoxyalkylene-modified polydimethylsiloxane compounds, but they are often used for the purpose of imparting antistatic properties and flexibility, and depending on the composition structure, they are not compatible with the acrylic main material. It is good, but since it does not have a reactive group, it is not immobilized in the main material, so it cannot be expected that the effect will last for a long time. Also,
Although the modified polydimethylsiloxane compound is further modified with a reactive epoxy group or amino group so that it can be immobilized on the main material, an acrylic material (eg, acrylic ester) is available. No polyoxyalkylene-modified polydimethylsiloxane compound that can be added to and copolymerized by radiation has been found yet.

In view of the above-mentioned conventional problems, the present invention is a novel material useful as an additive to a hard coating film material or the like which has high water repellency while maintaining high hardness and is unlikely to adhere dust. Modified polysiloxane compound, and a radiation-curable composition containing the same, which is useful for a similar hard coating film material and the like.

[0014]

In order to achieve the above object, the present invention proposes a novel modified polysiloxane compound represented by the following general formula.

[0015]

[Chemical 4]

(Wherein R ₁ and R ₂ are H or a methyl group, and 0 ≦ x ≦ 200, 4 ≦ y ≦ 30, 1 ≦ z ≦ 40, 1 ≦ j
≦ 50. In addition, in order to achieve the above object, the present invention proposes the following composition. That is, a radiation curable composition containing a novel modified polysiloxane compound represented by the following general formula is used.

[0017]

[Chemical 5]

(Wherein R ₁ and R ₂ are H or a methyl group, and 0 ≦ x ≦ 200, 4 ≦ y ≦ 30, 1 ≦ z ≦ 40, (y +
z) /x≧0.25 and 5 ≦ j ≦ 20. ) By adding the novel modified polysiloxane compound according to the present invention, the plastic can be modified, and added to a radiation-curable resin or a radiation-curable composition containing the same to obtain a copolymer. By doing so, the compound can be immobilized and the effect can be sustained.

Furthermore, a material containing a monomer having three or more acryloyl groups or methacryloyl groups contains, for example, 0.1 to 5 parts by weight of an acryloyl or methacryloyl- and polyoxyalkylene-modified polysiloxane compound represented by the following general formula. Let it be configured to.

[0020]

[Chemical 6]

(Wherein R ₁ and R ₂ are H or a methyl group, and 0 ≦ x ≦ 200, 4 ≦ y ≦ 30, 1 ≦ z ≦ 40, (y +
z) /x≧0.25 and 5 ≦ j ≦ 20. Here, the monomer having three or more acryloyl groups or methacryloyl groups is trimethylolpropane triacrylate, or an alkylene oxide-modified acrylate compound thereof (for example, triacrylate or trimethylolpropane of a 3 mol ethylene oxide adduct of trimethylolpropane). 3 mole propylene oxide adduct of triacrylate, etc.), trimethylolpropane trimethacrylate,
The alkylene oxide modified methacrylate compound (for example, trimethacrylate of trimethylolpropane adduct with 3 moles of ethylene oxide and trimethacrylate of adduct of trimethylolpropane with 3 moles of propylene oxide), pentaerythritol triacrylate, pentaerythritol trimethacrylate, penta At least one of erythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol heptaacrylate, dipentaerythritol heptamethacrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexamethacrylate may be used.

That is, for example, the hardness can be further increased by using a trifunctional structure rather than a bifunctional structure to form a mesh structure. Further, the radiation curable composition may contain a photopolymerization initiator for ultraviolet curing, for example, 3 to 15 parts by weight. The radiation-curable composition is preferably a solvent-free system, has a transparent film quality after curing, and has a pencil hardness of 2H or more.

Further, the radiation curable composition may contain, for example, 0.3 to 15 parts by weight of an antistatic reactive surfactant. Further, when the radiation curable composition is used as a hard coating film material for an optical disc, 2 ≦
x ≦ 200 is preferable. The novel modified polysiloxane compound according to the present invention is suitable as an additive to a radiation curable resin for a hard coating film material of an optical disc.

In this case, it is essential that the (meth) acrylic base material used is a (meth) acrylic acid ester monomer having three or more polymerizable functional groups from the viewpoint of forming a film with high hardness. , Depending on its type,
Although the solubility of the (meth) acryloyl and polyoxyalkylene-modified polysiloxane compounds according to the present invention is slightly different, if (y + z) / x is 0.25 or more and j is 5 or more, the compatibility with the acrylic base material is good. When (y + z) / x is less than 0.25, it tends to be emulsified or phase-separated depending on the value of j.

When j is more than 20, when (meth) acryloyl and polyoxyalkylene-modified polysiloxane compounds are added to the (meth) acrylic main material and radiation-cured, a film is formed due to a long polyoxyalkylene chain. Hardness is reduced. On the other hand, when the polyoxyalkylene is not modified (that is, j = 0), the selection range of the (meth) acrylic base material that gives a high crosslink density is narrowed, and the compatibility is inferior to the compound of the present invention.

If y is less than 4, the number of repetitions (x +
Although it depends on (y + z), the crosslink density becomes low, which is not desirable. Further, when y exceeds 30, gelation is very likely to occur during preparation of the (meth) acryloyl- and polyoxyalkylene-modified polysiloxane compound, which is disadvantageous in terms of productivity and the number of repetitions (x + y + z). However, the water repellency tends to deteriorate because the relative amount of the methylsiloxane component decreases.

The compound according to the present invention can be obtained from a compound obtained by hydrogen-modifying a part of side chain methyl of a polydimethylsiloxane compound represented by the following general formula.

[0028]

[Chemical 7]

By appropriately selecting x and k (= y + z) in the formula, it is possible to obtain a modified polysiloxane compound having various chain lengths and various degrees of modification with hydrosilyl groups, which are suitable for the above various conditions. .. Further, by setting the amount of polyoxyalkylene glycol monoallyl ether with respect to allyl acrylate (or allyl methacrylate) at the stage of charging the reaction raw material, a polysiloxane having an arbitrary modified composition can be synthesized.

That is, a certain set amount of polyoxyalkylene glycol monoallyl ether is mixed with the hydrosilyl group of the compound represented by the formula (7) to make a homogeneous system with a mixed solvent of toluene and tetrahydrofuran. Potassium acetate and platinum catalyst are added, and allyl group is added to hydrosilyl group at 40 to 60 ° C.

The reason for adding potassium acetate is to suppress the reaction between the hydroxyl group at one end of the polyoxyalkylene glycol monoallyl ether and the hydrosilyl group.
After allowing the reaction to proceed sufficiently, allyl acrylate (or allyl methacrylate) is added and mixed, and the addition reaction of the allyl group to the hydrosilyl group is further advanced. The total of allyl groups of the mixed polyoxyalkylene glycol monoallyl ether and allyl acrylate (or allyl methacrylate) is preferably about 1.2 equivalents with respect to the hydrosilyl group.

The platinum catalyst in the obtained compound solution is adsorbed and removed with activated carbon, and the toluene or tetrahydrofuran solvent and excess allyl acrylate or allyl methacrylate are removed under reduced pressure at 30 ° C. or lower. Above 30 ° C, depending on the amount of modification of the hydrosilyl group and the polysiloxane chain length,
During the removal of the toluene or tetrahydrofuran solvent, the (meth) acryloyl and polyoxyalkylene-modified polysiloxane compounds have a high concentration and are easily gelled, making it difficult to purify the compounds.

Further, it is desirable to add a small amount of a polymerization inhibitor such as methylhydroquinone to prevent the polymerization of acryloyl group or methacryloyl group. A monomer having three or more (meth) acryloyl groups, which is a main material of the radiation curable composition according to the present invention, will be described. As a material containing a large number of (meth) acryloyl groups in one molecule,
Polyol polyacrylate, urethane acrylate,
Epoxy acrylate etc. are commercially available, but when used as a material for hard coating film of optical disc,
The hardness of the cured product is an important selection factor, and in order to achieve high hardness, a high crosslink density is required. Generally, a material having a smaller acryloyl equivalent gives a higher hardness film quality.

As an essential material for achieving such hardness, a polyfunctional and low molecular weight polyol (meth) acrylate material is desirable. Specifically, as described above,
Trimethylolpropane tri (meth) acrylate and its alkylene oxide-modified (meth) acrylate compounds (for example, tri (meth) acrylate of a 3 mol ethylene oxide adduct of trimethylolpropane and trimol of a 3 mol propylene oxide adduct of trimethylolpropane). (Meth) acrylate, etc., pentaerythritol tri (tetra) (meth) acrylate, dipentaerythritol hepta (hexa) (meth) acrylate, etc., and one or more of these materials may be selected and used.

Further, one or several kinds of other (meth) acrylate compounds may be mixed with these materials as long as the film quality of high hardness can be maintained. For example, the urethane acrylate and epoxy acrylate are not only difficult to use in a solventless system because of their high viscosity,
Despite being polyfunctional, the (meth) acryloyl equivalent is large and the film quality is not so hard by itself, but a small amount may be mixed for the purpose of imparting adhesion and flexibility.

In addition, the (meth) acrylate material of the selected low molecular weight polyol alone or in a mixture thereof,
A mixture to which another (meth) acrylate material is added in order to impart functionality often has a high viscosity. In this case, in order to reduce the viscosity in order to improve the coating performance, a high hardness Within the range that can maintain the film quality, 1,
Bifunctional (meth) acrylates such as 6-butanediol di (meth) acrylate, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl ( A small amount of monofunctional acrylate such as (meth) acrylate and 2-hydroxyethyl (meth) acrylate may be mixed.

As the photopolymerization initiator, various commercially available initiators and sensitizers can be used. For example, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isobutyl ether,
Benzophenone, benzyl, benzyldimethylketal, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-benzoyl-
4'-methyldiphenyl sulfide, 3,3'-dimethyl-4-methoxybenzophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl ) -2-Hydroxy-2-methylpropan-1-one, 2-methyl- [4- (methylthio)
Phenyl] -2-morpholino-1-propanone, 2-
Chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and the like, and those in which these are used in combination with a sensitizer such as amines.

As the reactive surfactant, a nonion having an acryloyl group or a methacryloyl group in the molecule,
Cationic, anionic or betaine type surfactants can be used, but from the viewpoint of antistatic property,
Cationic surfactants are desirable, such as 2-methacryloylethyltrimethylammonium chloride, 2
-Hydroxy-3-methacryloxypropyltrimethylammonium chloride, 2-hydroxy-3-methacryloxypropylstearylammonium chloride and the like can be mentioned, but in that case, compatibility with the (meth) acrylate-based material blend of the main material Need to pay attention to.

[0039] Usually, simply mixing a reactive cationic surfactant into a (meth) acrylate-based material formulation is not very compatible and is not suitable for a clear coat. However, by selecting the (meth) acrylate material composition and optimizing the compounding method,
This problem can be solved. That is, after mixing and dissolving a reactive cationic surfactant in a hydrophilic acrylate material such as 2-hydroxyethyl acrylate, a trifunctional compound having a residual hydroxyl group such as pentaerythritol triacrylate and having a stronger hydrophilicity is prepared. When mixed with the above acrylate materials, an acrylate material formulation containing a reactive cationic surfactant can be obtained.

Even in this case, since the hardness is lowered by the addition of the reactive cationic surfactant or 2-hydroxyethyl acrylate, the acrylate-based material maintaining the hardness above a certain level (pencil hardness 2H). Must be a formulation of the composition. The acrylate material composition having such a composition has radiation (particularly ultraviolet) curability, the film quality after curing is transparent, and high hardness (pencil hardness 2H).
In the above), it is water-repellent, and when it is mixed with a reactive cationic surfactant, it also has an antistatic property and is useful as a hard coating material for plastics and the like.

Further, by optimizing the polysiloxane compound and the reactive cationic surfactant in terms of the structure and the compounding method, the compatibility can be improved and the solvent-free system can be obtained. Is very advantageous in terms of safety and
Further, since the solvent removal by heating is unnecessary, the process can be simplified, which is also very advantageous in this respect. Also,
When a hard coating film for an optical disc is formed by the radiation curable composition according to the present invention, this film is excellent in water repellency, and therefore, excessive adsorption of water on the film surface under high humidity conditions is reduced, and therefore stickiness is reduced. Adhesion of dust and dirt due to is reduced, and the bit error rate is reduced.

When a reactive cationic surfactant is also included, the surface resistance in a normal environment is reduced, so that the adsorption of dust and dirt due to charging is reduced, and in this respect also, the bit error rate is small. Become. In addition to being transparent with a high hardness (for example, a pencil hardness of 2H or more), it also has lubricity due to the dimethylpolysiloxane unit, so even if the hard coating film is rubbed, scratches can be prevented, and bits caused by scratches can be prevented. It has an extremely excellent characteristic that an error hardly occurs.

Furthermore, since it is UV-polymerizable and solvent-free, the film forming process is simplified.

[0044]

EXAMPLES Examples of the present invention will be described below. Synthesis Example of Compound 1 As the hydrogen-modified polysiloxane compound represented by the general formula of Chemical formula 7, XF40-A2346 (manufactured by Toshiba Silicone Co., Ltd.) having an average composition of x = 12 and k = 12 is used. This is 10 parts by weight, polyethylene glycol monoallyl ether (on average, 10 moles of ethylene oxide to allyl alcohol (j = 10), this is referred to as EO10, and this is related to Z) 20.26 parts by weight, Toluene 20
Parts by weight, tetrahydrofuran THF 30 parts by weight, and methylhydroquinone 0.018 parts by weight are mixed and stirred in a Kolben under a nitrogen atmosphere.

Thereafter, 0.025 parts by weight of a 10% ethanol solution of potassium acetate and 0.028 parts by weight of a 10% isopropyl alcohol solution of hexachloroplatinic (IV) acid hexahydrate are added as a reaction catalyst, and the temperature is raised to 60 ° C. The reaction was terminated in 10 hours while monitoring the decrease progress of the unreacted residual amount of hydrosilyl group (around 2155 cm ⁻¹ ) by infrared absorption spectrum.

The obtained reaction solution was treated with a CDCl ₃ solvent,
When the nuclear magnetic resonance spectrum ( ¹ H-NMR) is measured,
Since there was a peak due to Si—CH ₂ near 0.6 PPM, it was found that the addition reaction of the allyl group to the hydrosilyl group occurred. Then, this reaction solution
Allyl methacrylate AMA (related to y)
Add and mix 5.13 parts by weight.

The reaction was terminated 7 hours after the peak of the hydrosilyl group disappeared from the infrared absorption spectrum. After cooling to room temperature, add activated carbon and stir for about 1 hour.
After diluting with 30 parts by weight, suction filtration was performed with a 0.8 μm polytetrafluoroethylene membrane filter.

Toluene, tetrahydrofuran solvent and unreacted allyl methacrylate in the obtained compound solution are removed under reduced pressure by a vacuum pump. In this case, since the methacryloyl- and polyoxyalkylene-modified polysiloxane compound becomes high in concentration with the removal of the toluene and tetrahydrofuran solvent, when the solvent is depressurized while being heated to over 30 ° C, gelation is very likely to occur. , Need to be careful.

The ¹ H-NMR of the obtained methacryloyl- and polyoxyalkylene-modified polysiloxane compound is shown in FIG. 1, and the infrared absorption spectrum (IR) is shown in FIG. For comparison, ¹ H-N of the hydrogen-modified polysiloxane compound (XF40-A2346), which is the raw material, was used.
The MR spectrum is shown in FIG. 3 and the IR spectrum is shown in FIG.

Before and after the reaction¹H-NMR spectrum (Figure
1, 3) are compared, in FIG.
The peak around 4.7PPM due to H disappears (see Fig. 3).
E, 0.6PPM (Si-CH₂-), 1.65PPM (Si
-CH ₂ -CH₂-), 3.4PPM (-OCH₂CH₂
-OCH₂-CH ₂ -OH), 3.6PPM (-OCH ₂
CH ₂ -OCH ₂ -CH₂-OH), 3.7PPM (Si
-CH₂CH₂-CH ₂ -OCH₂CH₂-), 4.1P
PM (Si-CH₂CH₂-CH ₂ -OCO-), 1.9
PPM (CH₂= C (CH ₃ ) -COO-), 5.6 and
 6.1PPM (CH ₂ = C (CH₃) -COO-)
Appears and polyethylene from these to hydrosilyl groups
Glycol monoallyl ether and allyl methacrylate
It is clear that the addition reaction of
When two types of H with different electronic environments are listed in
Is underlined in H indicating the chemical shift
Separated. ).

Further, comparing the IR spectra before and after the reaction (FIG. 2 and FIG. 4), 2155 cm ⁻¹ due to Si—H
Disappeared peaks, also from the fact that peaks of methyl group and methylene group in the vicinity of 2960 cm ^-1, ester bond near 1720 cm ^-1, a peak derived from a C = C of methacrylic groups in the vicinity of 1640 cm ^-1 is occurring I understand. Synthesis Examples of Compounds 2 to 13 As shown in FIG. 5 (Example) and FIG. 6 (Comparative Example) (FIG.
In addition, the compound 1 is also described), and the x and k values of the hydrogen-modified polysiloxane compound (raw polysiloxane) represented by the general formula of Chemical formula 7 are changed to change the repeating number of the polysiloxane and the modification amount of the hydrosilyl group. Let's
Allyl (meth) acrylate (related to y) and polyoxyalkylene glycol monoallyl ether (related to z)
The amount of the raw material charged, the number of repetitions of polyoxyalkylene glycol monoallyl ether (related to j) and the type of alkylene (acryloyl group or methacryloyl group, and oxyethylene ether chain or oxypropylene ether chain) are changed (meta ) Acryloyl- and polyoxyalkylene-modified polysiloxane compound 2
Adjusted ~ 13.

In the figure, AA is allyl acrylate, EO2 is diethylene glycol monoallyl ether (j = 2), EO5 is polyethylene glycol monoallyl ether (j = 5), and EO15 is polyethylene glycol monoallyl ether ( j = 15), EO25 is polyethylene glycol monoallyl ether (j = 25),
PO10 represents polypropylene glycol monoallyl ether (j = 10).

The experimental synthetic method and the purification method are the same as those of the compound 1 described above, although the amounts of the catalyst and the amount of the diluting solvent are slightly different. Since the amount of hydrosilyl groups is different in each raw material polysiloxane, the total amount of allyl groups of allyl (meth) acrylate and polyoxyalkylene glycol monoallyl ether to be mixed is 1.2 equivalents to 1 equivalent of hydrosilyl group. I did it.

As in the case of Compound 1, the addition reaction of the allyl group to the hydrosilyl group has occurred for each raw polysiloxane compound and each modified polysiloxane compound synthesized by ¹ H-NMR spectrum and IR spectrum. It was confirmed. Here, for compounds 9 and 10, the raw material charges of allyl methacrylate and polyoxyalkylene glycol monoallyl ether were changed so that compound 9 was z = 0, j = 0, and compound 10 was y = 2. Compound 11,
12 is the number of repetitions of polyoxyalkylene glycol monoallyl ether, compound 11 is j = 2, compound
12 has j = 25. For Compound 13, the number of repetitions and the modification amount of the hydrosilyl group were changed to (y + z) /x=0.13. In other words, the compounds 9 and 10 do not meet the conditions of claim 1 of the present invention, and the compounds 11 to 13 are defined by claim 2.
It is given as an example that does not satisfy the condition of.

Next, compounds 1 to 13 were synthesized (meth)
Various properties when an acryloyl- and polyoxyalkylene-modified polysiloxane compound is added to a poly (meth) acrylate material as a base material will be described. Figure 7
The results of the compatibility investigation are shown in. That is, compound 1
(Meth) acryloyl and polyoxyalkylene-modified polysiloxane compounds obtained in any of 13 to 13 are used as the main material of the hard coating film, trimethylolpropane triacrylate (TMPTA), and propylene oxide 3 mol addition trimethylolpropane triacrylate ( T
MPTA-PO), triacrylate of trimethylolpropane with 3 moles of ethylene oxide (TMPTA-E)
O), pentaerythritol triacrylate (PET
1% each was added to TA) and dipentaerythritol hexaacrylate (DPETHA), and the state was observed.

In the figure, ◯ indicates transparent dissolution, Δ indicates translucent emulsification, and X indicates phase separation. From this result, the oxyalkylene chain length j is 5 or more, and the ratio of (y + z) / x is 0.25 or more (compounds 1 to 1).
It can be seen that the compatibility with all of the five types of polyfunctional acrylates is good in Nos. 8, 10, 12).

If the compatibility is not perfect, a transparent hard coating film cannot be obtained after curing, and it is unsuitable for use as a hard coating film for an optical disk. In Compound 9, polyoxyalkylene is not modified (z = 0, j = 0), in Compound 11, the oxyalkylene chain length j is as short as 2, and in Compound 13, (y +
The ratio z) / x is as small as 0.13, and the degree of modification is small, which is a factor of deterioration of compatibility.

FIG. 8 shows the results of investigating the water repellency of the system having good compatibility. That is, the same five kinds of main materials (TMPTA, TMPTA-PO, TMPTA-
EO, PETTA, and DPETHA) (99 parts by weight), 1 part by weight of (meth) acryloyl and polyoxyalkylene-modified polysiloxane obtained from compounds 1 to 8, 10, and 12, and Irgacure as a photopolymerization initiator.
500 (manufactured by Ciba Geigy) (with benzophenone
-Equivalent mixture of hydroxycyclohexyl phenyl ketone) 5 parts by weight is added and mixed, and this is uniformly applied on a polycarbonate plate in a thickness of about 10 μm and cured by ultraviolet rays to form a hard coating film, and a hard coating film is formed on this film. ,
Water repellency was evaluated by dropping 5 microliters of water in an environment of 20 ° C. and humidity of 70% RH and measuring the contact angle of the water droplets.

For comparison, a hard coating film containing no (meth) acryloyl or polyoxyalkylene-modified polysiloxane was also examined in the same manner.
Also, in the figure, numbers indicate contact angles, and the unit is (°). From these results, it can be seen that the contact angle is increased and the water repellency is improved by adding a small amount of (meth) acryloyl and polyoxyalkylene-modified polysiloxane.

Further, with Compound 10, the amount of methacryloyl modification is small (y = 2) and the proportion of polyethylene glycol increases accordingly (z = 10), so that it becomes more hydrophilic and the contact angle value does not become so large. It was On the other hand, the compound
Also in 12, the polyethylene glycol chain length j was 25, which was extremely hydrophilic on average, and the proportion of the polyethylene glycol component in the entire compound was high, so that the contact angle value was not so large.

Further, the addition amount of the compounds 1 to 8, 10 and 12 is 1
When it was%, the hardness was not so much affected as compared with various main materials alone (containing Irgacure 500), but when it was 5%, the hard coating films of compounds 10 and 12 were considerably softened. This is because the crosslinking density of the hard coating film was lowered by adding the compounds 10 and 12.

FIG. 9 shows two main materials (TMPTA and PE).
For the system in which compound 2 was added to each of TTA),
The results of examining the concentration (addition amount) dependence on water repellency (contact angle) and hardness (pencil hardness) are shown. 20 ℃, 70% humidity
5 microliters of water was dropped under the environment of RH, and the contact angle of the water droplet was measured to evaluate the water repellency. IRGAGUAR 500 (manufactured by Ciba Geigy) as a photopolymerization initiator
Parts by weight were mixed and uniformly coated on a polycarbonate plate to a thickness of about 10 μm, and cured by ultraviolet rays to form a hard coating film.

According to this, it can be seen that the addition of 0.1 parts by weight or more has a considerably water-repellent effect. Further, when the amount of addition is about 8 parts by weight, the pencil hardness may be less than 2H, and it can be said that the addition amount of (meth) acryloyl and polyoxyalkylene-modified polysiloxane compound is preferably 0.1 to 5 parts by weight. FIG. 10 shows the results of examining the concentration dependence of Compound 2 on the antistatic property and the like when Compound 2 was added to a commercially available product.

That is, a UV curable composition containing a monomer containing a reactive cationic surfactant and having 3 or more (meth) acryloyl groups can be obtained as a hard coating material from other companies. Yes,
For example, RC-003 and RC-005 of Nippon Kayaku Co., Ltd. may be mentioned. These materials are based on pentaerythritol triacrylate, other trifunctional or higher functional acrylates, bifunctional acryloyl reactive diluents, antistatic reactive cations, and hydrophilic acryloyl reaction for dissolving reactive cations. And a photopolymerization initiator.

With respect to the system in which the compound 2 was added to the above-mentioned reactive cationic surfactant-containing UV-curable composition RC-003, the antistatic performance (surface resistance value and half-life as evaluation items) was measured with the addition concentration as a parameter. ), Water repellency (contact angle value as an evaluation item) and pencil hardness are shown. The surface resistance and half-life are measured in an environment of 23 ° C. and a humidity of 50% RH, and the contact angle is measured in an environment of 20 ° C. and a humidity of 70% RH by dropping 5 microliters of water. I went.

Since the photopolymerization initiator was added to the composition in advance, no new addition was carried out. Uniformly apply about 10 μm to a polycarbonate plate, and irradiate with ultraviolet rays (1600 mj / c
It was cured by m ² ) to form a hard coating film. According to this, it can be seen that the surface resistance value, which is one of the parameters showing the antistatic property, becomes slightly smaller with the addition amount of the compound 2. This is due to the polyoxyethylene chain.

Further, the half-life showing the antistatic property tends to decrease with the addition amount, which is considered to be the same reason. On the other hand, with respect to water repellency, the effect of the contact angle value becomes considerably large with the addition of a small amount and the effect is remarkable. Even in this case, if the amount added is as large as 8 parts by weight, the pencil hardness will be less than 2H and scratches will occur easily. Therefore, the addition of the methacryloyl and polyoxyalkylene-modified polysiloxane compound is preferably up to 5 parts by weight.

[0068]

As described above, the specific (meth) acryloyl- and polyoxyalkylene-modified polysiloxane compound according to the present invention is a radiation-curable composition for a hard coating film of an optical disk (a main material is a specific ( When used as an additive to (meth) acrylic materials,
In addition to having compatibility with the main material of the composition, it contains an acryloyl group or methacryloyl group that can be immobilized by copolymerization with the main material, and further contains a methyl siloxane component having water repellency. When a hard coating film such as an optical disc is formed by using a radiation curable composition containing the compound according to the above 1, the transparency, water repellency and hardness are excellent, and these performances are retained for a long period of time. It can be a membrane that can be.

Since the compound according to the present invention also has lubricity, scratches can be prevented even if dust on the hard coating film is wiped off.

[Brief description of drawings]

FIG. 1 is an NM of a product compound according to Compound 1 of the present invention.
R spectrum diagram

FIG. 2 is an IR spectrum diagram of the compound produced above.

FIG. 3 is an NMR spectrum diagram of a raw material compound according to Compound 1.

FIG. 4 is an IR spectrum diagram of the above raw material compound.

FIG. 5 is a diagram showing reaction conditions of compounds 1 to 8 and their constitutions.

FIG. 6 is a view showing reaction conditions of compounds 9 to 13 and their constitutions.

FIG. 7 is a diagram showing the compatibility of compounds 1 to 13

FIG. 8 is a diagram showing water repellency of a radiation curable composition.

FIG. 9 is a graph showing concentration dependence of Compound 2 on water repellency and hardness.

FIG. 10 is a diagram showing the concentration dependence of Compound 2 with respect to the charging property and the like when the main material of the composition is a commercial product.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical display location C08K 5/17 C08L 83/10 LRT 8319-4J G11B 7/24 536 7215-5D

Claims (8)

[Claims] 1. A novel modified polysiloxane compound represented by the following general formula. [Chemical 1] (In the formula, R ₁ and R ₂ are H or a methyl group, and 0 ≦ x
≦ 200, 4 ≦ y ≦ 30, 1 ≦ z ≦ 40, and 1 ≦ j ≦ 50. ) 2. A radiation-curable composition containing a novel modified polysiloxane compound represented by the following general formula. [Chemical 2] (In the formula, R ₁ and R ₂ are H or a methyl group, and 0 ≦ x
≦ 200, 4 ≦ y ≦ 30, 1 ≦ z ≦ 40, (y + z) / x ≧ 0.
25 and 5 ≦ j ≦ 20. ) 3. A radiation-curable composition containing a monomer having three or more acryloyl groups or methacryloyl groups and a novel modified polysiloxane compound represented by the following general formula. [Chemical 3] (In the formula, R ₁ and R ₂ are H or a methyl group, and 0 ≦ x
≦ 200, 4 ≦ y ≦ 30, 1 ≦ z ≦ 40, (y + z) / x ≧ 0.
25 and 5 ≦ j ≦ 20. ) 4. The monomer having three or more acryloyl groups or methacryloyl groups is trimethylolpropane triacrylate, an alkylene oxide modified acrylate compound thereof, trimethylolpropane trimethacrylate, an alkylene oxide modified methacrylate compound thereof, pentaerythritol triacrylate, Characterized by comprising at least one of pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol heptaacrylate, dipentaerythritol heptamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate The radiation curable composition according to claim 3. 5. A radiation curable composition comprising the radiation curable composition according to claim 2 or 3 containing a photopolymerization initiator for ultraviolet curing. 6. A radiation curable composition, characterized in that the radiation curable composition according to claim 2 or 3 is a solventless system, has a transparent film quality after curing, and has a pencil hardness of 2H or more. Composition. 7. A radiation-curable composition comprising the radiation-curable composition according to claim 2 or claim 3 and a reactive surfactant for antistatic contained therein. 8. A radiation-curable composition comprising the radiation-curable composition according to claim 2 or 3 as a hard coating film material for an optical disk.