JP2508817B2 - Synthetic resin molding manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a synthetic resin molding aid comprising a specific organopolysiloxane / polyoxyalkylene block copolymer, and a synthetic resin produced using such an aid. The present invention relates to a method for manufacturing a molded product.

[Prior Art] The production of wax products, rubber products, plastic products, etc. made of reaction-curable resins such as polyurethane resins, polyurea resins, polyurethaneurea resins, polyisocyanurate resins, etc., first involves mixing the polyisocyanate component and the polyol component. A method is employed in which a reactive precursor such as a body is formed, and then a polymerization reaction of the precursor is allowed to proceed to produce the precursor. It is also possible to use a method of producing a product by simultaneously advancing resin generation and molding, and a reaction injection molding method or a reactive casting method has been put into practical use.

For example, the reaction injection molding method is a method in which two or more kinds of raw materials that are reactive with each other are rapidly impinged and mixed to produce a reactive precursor, which is then charged into a molding die at a high speed for reaction curing.
It is a method of finishing into a molded body. The reactive casting method is a method in which a reactive precursor is cast on a suitable carrier and then cured by reaction, and the carrier is removed to produce a sheet-shaped molded product.

Since these methods produce, cure, and mold the synthetic resin with the reactive precursor in direct contact with the surface of the substrate, they often cause various problems due to the behavior of the precursor at the contact surface. I was letting it. In general, an injection molding die or a casting carrier is used by subjecting the surface of the base material to a release treatment with a silicone compound or a fluorine compound. These compounds are widely used as a general-purpose mold release agent because they are not easily compatible with the hydrocarbon compounds that normally form a molded body and can easily separate the base material and the molded body. However, on the other hand, since these do not match with the precursor to be molded, the precursor surface in contact with the base material surface is greatly disturbed, and as a result, a problem of causing defects such as so-called yuzu skin on the surface of the molded product is caused. I was there.

Such problems are subject to serious defects, especially in reactive casting processes. This is because in this case, the turbulence generated at the contact interface easily spreads throughout the cast precursor, resulting in a large "repellency", which makes it difficult to manufacture a good product. is there.

In recent years, the reactive casting method has been attracting a great deal of attention because a homogeneous sheet-like product excellent in mechanical strength can be obtained (Japanese Patent Publication No. 57-59815, Japanese Patent Laid-Open No. 60-48312,
JP-A-56-162618 and JP-A-55-105534). Of particular interest to the inventors was also the production of transparent sheets without optical defects made by such a method. The present inventors have attempted to produce a transparent plastic sheet having a layer of the reaction-curable composition (Japanese Patent Application No. 62-60107) having a high surface performance disclosed above as a surface layer and faced such a difficulty. .

It is known that problems such as "repellency" that occur during the molding of reaction-curable resins can often be dealt with by adding auxiliary agents such as flow agents and leveling agents that improve the flowability and wettability of the substrate surface. Has been. It is considered that all of these are effective for uniformly spreading the cast precursor because they weaken the cohesive force between molecules and enhance the flowability and the slip property. Generally, a silicone compound or a fluorine compound, which can be expected to have a high effect with a small addition amount, is used. However, as described above, these compounds are difficult to be compatible with the hydrocarbon-based resin, so that it was often found that they were not mixed with each other, or even if they were temporarily mixed, they bleed out after a while. Therefore, in order to avoid such a phenomenon, an attempt to chemically bond the polymer matrix forming the synthetic resin and the additive was also studied.

Many of the silicone compounds having a reactive group are known, and there are many commercially available products. For example, JP-A-62-257966,
JP-A-62-257965 and JP-A-62-167785 describe organic polysiloxane compounds having an NCO-group.
JP 62-227423 and in JP 62-216624, etc. NH ₂ - organopolysiloxane compound having a group is described.
Further, JP-A-62-225516, JP-A-62-131009, JP-A-62-62100
-45667 and the like describe an organic polysiloxane compound having an OH- group. Since all of these can be chemically bonded in the urethane resin matrix,
It is expected that the above concerns will be resolved. Therefore, among these, compounds that could be synthesized and commercially available similar compounds were obtained, and the effect of preventing "repellency" was examined. However, none of these has been found to exhibit a satisfactory preventive effect.

Similarly OH- group, COOH-group, NH ₂ - fluorine-based compound having a group are also known, are readily available.
However, none of these could be found to function effectively in the prevention of “repellency”.

On the other hand, increasing the wettability of the contact interface with a surfactant is also considered to be an effective means for preventing "repellency". Japanese Patent Application No. 62-64249 describes that it is possible to prevent "repellency" between the urethane resin and the substrate by using a polyisocyanate compound modified with a fluorosurfactant. When such a method was used for forming a film of the above reaction curable composition, it was found that it was an effective means for preventing "repellency", but the composition cured film had particularly excellent scratch resistance. It has also been found that it has a drawback that it is greatly reduced. Furthermore, there is a drawback that the coating may be whitened due to the fact that the composition is a cross-linking type, or the coating containing more than 0.5 wt% of a fluorosurfactant is not admitted. Was judged.

The silicone-based surfactant was also examined by the same method as in the case of the fluorine-based surfactant. The available silicone-based surfactants can be roughly divided into two groups. One is a block type structure having polyoxyalkylene chains at both ends of polydimethylsiloxane chain.
The other one has a graft type structure having a polyoxyalkylene chain branched to a polydimethylsiloxane chain. As for the prevention of "repellency", it was found that a graft type one with an average molecular weight of about 500 to 5000 is effective, but all of those judged to be effective have a large scratch resistance of the cured film. It had the drawback of being reduced to. On the other hand, the block type does not have much adverse effect on the scratch resistance of the cured film, but it has almost no effect on the prevention of "repellency", and it has a drawback that many of them cause the cured film to whiten. I understood.

[Problems to be Solved by the Invention] As described above, molding aids that have been considered to be effective in preventing "repellency" in molding have not been suitable for reactive casting of urethane resin. Many, and those judged to be effective in preventing "repellency" also have a problem that the scratch resistance, which is one of the important surface performances of the cured coating, is greatly reduced. It was a thing.

The present invention aims to solve the above-mentioned problems and to provide a novel molding aid which suppresses "repellency" during molding and does not adversely affect the surface performance of a cured coating.

[Means for Solving the Problems] The present invention is the following inventions relating to a novel auxiliary agent for solving the above problems and a method for producing a synthetic resin molded article using the same.

Diorganosiloxane unit having no polyoxyalkylene chain (A), diorganosiloxane unit having polyoxyalkylene chain (B), optionally present 3
To tetrafunctional siloxane units (C), and at least two terminal triorganosiloxane units (D), at least one of which terminal organoorganosiloxane units (D) reacts with its organic groups with isocyanate groups. Of an organopolysiloxane / polyoxyalkylene graft copolymer having a functional group capable of reacting, containing a synthetic resin molding aid for improving wettability to a substrate by adding to a synthetic resin or a precursor, by reaction curing A method for producing a synthetic resin molded article, which comprises subjecting a reactive precursor capable of forming a synthetic resin to reaction curing while contacting with a substrate having a releasable surface.

The above-mentioned auxiliary agent of the present invention is used by adding it to a fluid synthetic resin or a precursor thereof which solidifies or cures in a state of contacting with a substrate having a releasable surface to become a solid synthetic resin.
As the fluid synthetic resin, not only a molten synthetic resin or a synthetic resin solution but also a powdery synthetic resin or a synthetic resin dispersion liquid which is once melted and solidified on a substrate may be used. The synthetic resin precursor refers to a monomer that can be polymerized to form a synthetic resin or a mixture of at least two compounds that can be polycondensed to form a synthetic resin. Further, the flowable precursor may be a solid at the stage of being applied to the substrate as long as it can be fluidized on the surface of the substrate. Preferably, the flowable precursor is itself a liquid or a solution at the stage of application to the substrate.

The auxiliary agent of the present invention is particularly applied to a synthetic resin precursor, and the precursor is composed of a mixture of a compound having two or more functional groups reactive with an isocyanate group and a polyisocyanate compound. The polyisocyanate compound may be blocked with a blocking agent until the time of reaction. Further, the formation of the synthetic resin may proceed by other reaction in addition to the reaction between the functional group and the isocyanate group. As the functional group reactive with the isocyanate group, a hydroxyl group, a primary amino group, a secondary amino group, a carboxyl group, a mercapto group,
There are epoxy groups and the like, and particularly alcoholic hydroxyl groups and the above amino groups.

In the diorganopolysiloxane / polyoxyalkylene graft copolymer, the diorganosiloxane unit (A) having no polyoxyalkylene chain is represented by the following general formula (1) [In the formula, R ¹ and R ² represent the same or different hydrocarbon groups having 6 or less carbon atoms, halogenated hydrocarbon groups, or halocarbon groups. ]]. The diorganosiloxane unit (B) having a polyoxyalkylene chain is represented by the following general formula (2) [Wherein R ³ is selected from those allowed for R ¹ or R ² , and R ⁴ is an organic group having a polyoxyalkylene chain]. The optionally present 3- to 4-functional siloxane (C) is preferably a trifunctional monoorganosiloxane unit. Moreover, it is preferable that the number of the unit (C) is one, if any. The organic group bonded to the monoorganosiloxane unit is an organic group (R ⁵ ) selected from those allowed for R ¹ or R ² or an organic group (R ⁶ ) having a polyoxyalkylene chain. is there. The terminal triorganoximexane unit (D) is present in at least two units (when the unit (C) is not present), and is present in three or more units (D). Hereinafter, this unit (D) is represented by the general formula (4) [Wherein R ⁷ and R ⁸ are each selected from those allowed for R ^{1 and} R ² , and R ⁹ is an organic group having a functional group reactive with an isocyanate group or R ¹ Represents one selected from those allowed for R ² ]. In this formula, the oxygen atom bonded to the silicon atom means that the terminal group is present when it is bonded to the silicon atom of the unit and is absent when it is bonded to the oxygen atom. Furthermore, this 1
In at least one unit (D) having two or more units in the molecule, it is necessary that R ⁹ therein is an organic group having a functional group reactive with an isocyanate group. In addition, hereinafter, the number of units (A) in one molecule is a, the number of units (B) is b,
The number of units (C) is g, and the number of units (D) is h. a, b
Are integers of 1 or more, g is 0 or an integer of 1 or more, h is an integer of 2 or more, and preferably g is 0 or 1, and h is 2 or 3. The average number of these molecules per molecule may not be an integer. Further, when two or more of each unit are present in one molecule, R ^{1 to} R ⁹ may be different in each of the above units. For example, when the unit (A) is present 2 or more, R ¹ or R ² in a unit therein or R ¹ in the other units therein
May be different than R ² .

R ¹ and R ² in the above unit (A) preferably have 1 carbon atom.
2 is a hydrocarbon group selected from an alkyl group or a phenyl group, or a 3,3,3-trifluoropropyl group. It is particularly preferable that both R ¹ and R ² are methyl groups. R ³ , R ⁵ , R ⁷ and R ⁸ are also preferably these groups, especially a methyl group. R ⁴ is suitably an organic group having an alkylene group bonded to a silicon atom and a polyoxyalkylene chain following the other of the alkylene groups and a terminal group of the chain, and the terminal group is preferably a hydroxyl group or an alkoxy group. The polyoxyalkylene chain has 2 to 6 carbon atoms.
Is preferably a homopolymer chain of oxyalkylene groups, a random or block copolymer chain, and particularly preferably a polyoxyalkylene chain composed of oxyethylene groups and / or oxypropylene groups. More preferably, a polyoxyethylene chain and a poly (oxyethylene / oxypropylene) chain are preferable. This R ⁴ is represented by the general formula (5)
CH ₂ ) _d (OC ₂ H ₄ ) _e (OC ₃ H ₆ ) _f OX (where d is an integer of 1 ≦ d ≦ 4, e is an integer of 1 or more, f is 0 or an integer of 1 or more, and X is Those which are represented by a hydrogen atom or an alkyl group) are preferable. It should be noted that this formula does not mean only a block-like copolymer chain of oxyethylene groups and oxypropylene groups. Preferred X is an alkyl group having 8 or less carbon atoms, particularly 4 or less carbon atoms, and a methyl group is most preferred. The molecular weight of R ⁴ is preferably 5000 or less, and particularly preferably 3000 or less.
Further, d is preferably 2 or 3, and particularly preferably 3. The total sum of e + f is suitably from 2 to 50, particularly preferably from 3 to 30. Further, when the total of e + f is small, it is preferable that all or most of f is a very small number as compared with 0 to e. For example, even when e + f is large, the ratio of e / (e + f) is large. Is preferably 50% or more.

Two or more units (D) which are the terminal groups are present in one molecule, and R ^{7 to} R ⁹ represented by the general formula (4) may be different in each unit (D). However, R ⁹ in at least one of the units (D) must be an organic group having a functional group reactive with an isocyanate group (other R ⁹ is the same group as R ¹ or R ^2). preferable). Preferably, in the two units (D), R ⁹ thereof is an organic group having a functional group reactive with an isocyanate group (note that R ⁹ may be different). Most preferably,
R ^{9 in} all units (D) is such an organic group. Further, it is advantageous for producing the auxiliary agent of the present invention that R ^{7 to} R ⁹ in each unit (D) are the same. Therefore, all the units (D) are preferably the same triorganosiloxane except for the presence or absence of the oxygen atom of the general formula (4). However, as described below, when R ⁹ has a repeating unit, the number of the repeating units may be slightly different. Hereinafter, R ⁹ is an organic group having the above functional group.

R ⁹ has at least one functional group reactive with an isocyanate group as described above, and the functional group is preferably a hydroxyl group. As R ⁹ , a hydrocarbon group having a functional group,
In particular, it is an alkyl group having a functional group at or near the end, or has an oxyalkylene group, an ester group, or a polyoxyalkylene chain or polyester chain having a repeating unit thereof, and has a functional group at the terminal or near the end. Organic groups having groups are preferred. Particularly preferred R ⁹
Is the general formula (6) Is an organic group represented by. In this formula, R ¹⁰ represents a divalent hydrocarbon group having 20 or less carbon atoms, R ¹¹ represents an alkylene group having 2 to 8 carbon atoms, k represents 0 or 1, and m represents an integer of 0 or 1 or more. R ¹⁰ is preferably an alkylene group, and when m is 0, it preferably has 2 to 18 carbon atoms, particularly 4 to 14 carbon atoms. When m is not 0, R ¹⁰ may have a smaller number of carbon atoms, preferably 2-18, particularly preferably 2-8. R ¹¹ is preferably an alkylene group of 2 to 6, and particularly preferably an ethylene group, a propylene group, a 1,2-butylene group, a 2,3-butylene group, a pentamethylene group and the like. When k is 0, [] is an ether residue, and when k is 1, [] is an ester residue. When m is 2 or more, the types of residues in [] existing in 2 or more may be different, and in that case, k
It may be a combination of different materials. preferable Is a mono- or polyoxyethylene group, a mono- or polyoxypropylene group, a poly (oxyethyleneoxypropylene) group, and a mono- or polycaprolactone residue, that is, Is. The upper limit of m is not particularly limited,
It is preferably 50, especially 20.

As described above, the diorganopolysiloxane / polyoxyalkylene graft copolymer in the present invention has at least both a side chain having a polyoxyalkylene chain and an end group reactive with an isocyanate group in one molecule.
It is made of a special silicone compound. The unit represented by (A) plays a role of increasing the affinity of the synthetic resin for the surface of the substrate which is generally strongly hydrophobic, and contains at least 2 units per minute, preferably 5 units or more. It is desirable to prevent "repellency" and to form a smooth coating film without scratches. The unit represented by (B) serves as a unit for introducing a polyoxyalkylene side chain into the polysiloxane chain, but it lowers the interfacial tension between the surface of the base material and the synthetic resin to improve the resin for the base material. In addition to enhancing the wettability of the silicone resin, it also plays a role of uniformly dissolving the silicone compound, which is not familiar with the synthetic resin, even the relatively long-chain polysiloxane in the synthetic resin. Therefore, the introduction amount of the unit (B) should be determined depending on the length of the polysiloxane chain and the length of the polyoxyalkylene chain.
Generally, the ratio a of the number of units (A) to the number b of units (B) in one molecule is 1 ≦ a / b ≦ 25, and the number of chains of the unit (A) alone does not exceed 25. It is considered preferable to be decided. Further more preferably, the ratio is 2 ≦
It is desirable to be determined in the range of a / b ≦ 15 from the viewpoint that the auxiliary agent composed of such a compound can be uniformly dissolved in the synthetic resin and a smoother film can be formed. The side chain component in the unit (B) is formed by providing at least one oxyalkylene unit in one molecule with respect to the polysiloxane chain via 1 to 4 methylene groups. The chain length of such an oxyalkyllene group should be determined depending on the chain length of the polysiloxane, but in general, It is preferable that the above condition is satisfied and the average molecular weight per oxyalkylene chain is determined within a range not exceeding 5000.
The oxyalkylene chain may be formed from any oxyalkylene unit, but it is preferable that the oxyalkylene chain is formed from oxyalkylene having a carbon number not exceeding 3 in one unit, more preferably at least 1 in the chain.
It is desirable to have one oxyethylene unit in order to improve the compatibility between such a compound and the molding resin and the wettability between the substrate surface and the resin contact surface and to form a smoother transparent film. The side chain terminal in the formula (5) may be an OH-group or an alkyl group, but it is preferably stabilized with an alkyl group, which does not adversely affect the surface performance of the cured film. Desirable in terms.

The synthetic resin molding aid of the present invention effectively functions when it is applied to a process of manufacturing and molding through reaction curing of a polyurethane resin. In particular, when it is applied to the molding of a transparent polyurethane resin layer exposed on the surface of a molded product, its characteristics are greatly exhibited. The auxiliary agent of the present invention, even though it is a silicone compound as described above, dissolves well in a hydrocarbon-based polyurethane resin, and at the time of molding, "repellency" between the base material surface and the synthetic resin interface is prevented. To prevent
In the case of the molded product, the surface performance of the cured film is not deteriorated at all. This is a very interesting finding when the lengths of the siloxane chain and the chain other than the siloxane chain are fixed and the performances of the compounds having different structures are compared. For example, when a compound having a structure having a polyalkylene oxide chain having terminal OH-groups at both ends of a linear polysiloxane chain (hereinafter referred to as I-type) is used as an auxiliary agent, the surface performance of the cured film is deteriorated. Instead of causing less, the compatibility with the synthetic resin is impaired and whitened,
Moreover, a large "repellency" is generated at the contact interface with the substrate surface. On the other hand, when a compound having a structure in which a polyoxyalkylene chain having a terminal OH-group is provided by branching to a siloxane chain (hereinafter referred to as II-type) is used as an auxiliary agent, it is Although the "repellency" of the synthetic resin can be well prevented and high compatibility is exhibited, the surface performance of the cured coating is significantly reduced.

The present invention interprets such findings as follows. The surface performance of polyurethane resin is easily affected by the state of aggregation of urethane bonds. In the II-type, it was determined that the coil-shaped polysiloxane chain largely covers the vicinity of the urethane bond, so that the aggregation of the urethane bond is disturbed and the physical properties are greatly deteriorated. On the other hand, in the case of I-type, the polysiloxane chain has such an adverse effect and high surface performance is maintained as it is, but the resin is whitened because a single polysiloxane chain and the polyurethane resin matrix are incompatible. Was judged. Therefore, a compound having a structure in which an I-type form has a bonding group with a matrix and an alkylene oxide chain is branched in the II-type form (hereinafter referred to as III-type) is used as an auxiliary agent. Therefore, it is expected that the adverse effect on the surface performance can be eliminated, and the high compatibility and the effect of preventing "repellency" can be exhibited together.

The auxiliaries of the present invention have proved that such an expectation can be realized, and based on the structure of the III-type, which can bring out the advantages of the I-type and the II-type and be compatible with each other. It consists of a novel silicone compound. In addition, the one having an I-type bonding group with the synthetic resin matrix does not adversely affect the surface performance even if the OH-group remains at the terminal of the branched oxyalkylene chain. It was also found at the same time.

The following are examples of the auxiliaries used in the present invention.

It should be noted that in the following formula (the same applies to the compounds of Examples described later), it does not mean that divalent siloxane units such as the unit (A) and the unit (B) are linked in a block form. These are usually connected randomly. Similarly, in a polyoxyalkylene chain having two or more types of oxyalkylene groups, the oxyalkylene units are not necessarily linked in a block form, but are usually linked in a random form.

The silicone-type compounds specifically exemplified are mainly those described by Irgo et al. [Polym. Bull. 8 , 535 (1982)] and McGrath's [ACS Symposium Series No. 212, 145 (1).
983)] and the like.

The auxiliary agent of the present invention is used for the purpose of improving the moldability by adding it to the synthetic resin or the reactive precursor that reacts to form the synthetic resin as described above. As the synthetic resin, a synthetic resin having a bond generated by a reaction between an isocyanate group and a functional group reactive with an isocyanate group is preferable. In particular, it is used when forming a polyurethane or polyurethane urea obtained by reacting an active hydrogen-containing compound such as a polyol with polyisocyanate simultaneously with molding from a reaction curable precursor thereof. Examples of the reactive precursor include a mixture of an active hydrogen-containing compound such as a polyol and a polyisocyanate compound, a mixture of an isocyanate-terminated polyurethane prepolymer, a curing agent, a chain extender and the like.

The auxiliary agent of the present invention comprising such a compound or the like can be used as a mixture with a polyol component in molding a polyurethane resin. It can also be used in the form of being reacted with the polyisocyanate component in advance. Further, it can be added after the prepolymer is formed. Such an auxiliary is 0.02 to the synthetic resin component to be molded.
Although it can be added in the range of 30% by weight, it is preferably added in the range of 0.05 to 15% by weight from the viewpoint that a more uniform smooth film can be formed.

Further, the auxiliary agent of the present invention can be used in combination with other compounding ingredients which are generally added to polyurethane resins. As other compounding components, those which are usually used include organometallic compound-based catalysts such as organotin compounds and tertiary amine compound-based catalysts. Further, in order to reduce the viscosity of the reactive precursor, it is possible to use a solvent that can be removed during molding. Examples of the solvent include ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, propyl acetone, and cyclohexone, dioxane, butyl acetate, ethyl acetate, toluene, xylene, and other organic solvents. Further, as components that can be optionally mixed, for example, various ultraviolet absorbers, light stabilizers, stabilizers such as antioxidants, surface performance improvers such as surfactants and adhesion promoters, and colorants and plasticizers. , Flame retardants, etc.

The auxiliary agent of the present invention is used to produce a synthetic resin by using a precursor capable of forming a synthetic resin such as a polyurethane resin in a form of being in direct contact with a substrate, particularly a surface of a molding substrate that has been subjected to a mold release treatment.
When applied to the molding process where curing and molding are performed,
It expresses its function particularly effectively. That is, the reactive precursor prepared by the one-shot method or the prepolymer method is applied to the surface of the substrate by the casting method, the injection method, the spray method or the like, and is effectively used in the molding process. Since the auxiliary agent of the present invention has high compatibility with the polyurethane resin, it can be effectively used for molding a transparent body. In addition, since it does not adversely affect the surface properties such as high scratch resistance of the polyurethane resin, it is effectively applied to the molding of a transparent body exposed on the surface of the molded body. Of these, the most preferable application is the process for producing a transparent polyurethane resin molded body, which is carried out by the reactive casting method. That is, the reactive precursor of the polyurethane resin containing the auxiliary agent of the present invention, cast from a slit-shaped die and cured on a releasable substrate that is continuously conveyed, in the manufacturing process of a film-shaped molded body. is there. As a result, "repellency" with the base material is suppressed, so that a transparent smooth film that is homogeneous and has high surface performance has a thickness of 1 μm.
It can be manufactured in the range of up to 20 mm.

[Examples] Next, examples of the present invention will be described more specifically, but it goes without saying that the present invention is not limited to these examples.

Examples 1-5 and Comparative Examples 1-7 First, the silicone compounds A to L were prepared.

The effect of addition when such a compound was used as the following polyurethane resin molding aid was investigated. The results are shown in Table 1.
It was like.

-Polyurethane resin raw material Polyol component; Mixture 90 prepared with ε-caprolactone-based triol having an average molecular weight of 300,500,800 and an average equivalent molecular weight of 152
Parts, ε-caprolactone diol having an average molecular weight of 4000 10
Parts, and 0.5 parts of the silicone compound.

Isocyanate component: 99 parts of a mixture composed of 1,6-hexanediisocyanate and an isocyanurate modification product of 1,6-hexanediisocyanate and having an average equivalent molecular weight of 158.

-Evaluation of "Repelling" Preventing Property A polyol component and an isocyanate component were charged together with a catalytic amount of dibutyltin dilaurate, and the mixture was stirred and mixed under reduced pressure at 60 ° C for 4 minutes to obtain a reactive precursor. Next, using a knife coater, while moving the glass plate on which polydimethylsiloxane was baked at a speed of 20 cm / min, the precursor was applied onto the glass plate. After curing this at 120 ° C. for 15 hours, the ratio of the smooth coating area to the effective glass area was calculated to evaluate the “repellency” preventing effect of the auxiliary agent.

-Evaluation of the influence on the surface performance The reactive precursor, between the glass plate treated with γ-glycidoxypropylsilane and the glass plate baked polydimethylsiloxane, a spacer with a thickness of 0.5 mm It was then sandwiched and cured at 120 ° C. for 15 hours. After that, the plate glass treated with polydimethylsiloxane was removed to obtain a plate glass-urethane resin laminate in which the urethane resin layer was firmly adhered to the glass plate.
The urethane resin surface side of the laminate was measured for scratch resistance, haze, and taper resistance, and the effect of the addition of an auxiliary agent on the surface performance was evaluated.

Examples 6 to 7 and Comparative Examples 8 to 11 The addition effect of the molding aid was examined in the same manner as in Example 1 except that the urethane resin containing the following polyol component and isocyanate component was used. The results are shown in Table 2.
It was like.

-Polyurethane resin raw material Polyol component; 90 parts of a mixture prepared with ε-caprolactone-based triol having an average molecular weight of 300,500,800 and an average equivalent molecular weight of 146, and ε-caprolactone-based diol 10 having an average molecular weight of 4000
Part Isocyanate component: 46.5 parts of 1,6-hexane diisocyanate and 3.5 parts of a silicone compound were mixed and reacted under reduced pressure of 80 ° C. for 2 hours to obtain 5 parts of silicone-modified 1,6-hexane diisocyanate, and 1, 95 parts of a mixture of 6-hexane diisocyanate and an isocyanurate modification of 1,6-hexane diisocyanate, prepared to have an average equivalent molecular weight of 167.

[Advantages of the Invention] The auxiliary agent of the present invention is composed of a novel silicone compound having a specific structure, but when applied to molding a polyurethane resin, it prevents "repellency" on the contact surface with the substrate. Thus, it has an excellent effect that a uniform smooth coating film having no wrinkle skin can be produced, and that the surface performance such as high scratch resistance of the polyurethane resin is not adversely affected. Moreover, although the auxiliary agent of the present invention is composed of a silicone compound, it has a high compatibility with a hydrocarbon-based polyurethane resin due to its specific structure and can be applied to the production of transparent molded articles. Have Since the auxiliary agent of the present invention also contains a polysiloxane chain, it has the effect of making the resin surface less likely to be soiled, and also capable of relatively easily removing the soiled matter,
It was confirmed that it also has the effects of antifogging and antistatic properties, and the effect of enhancing the releasability between the resin and the substrate.

Claims (9)

(57) [Claims] 1. A diorganosiloxane unit (A) having no polyoxyalkylene chain, a diorganosiloxane unit (B) having a polyoxyalkylene chain, and a tri- or tetrafunctional siloxane unit (C) which may optionally be present. ), And at least two terminal triorganosiloxane units (D), at least one of the terminal triorganosiloxane units (D) having in its organic group a functional group capable of reacting with an isocyanate group. Reactivity capable of forming a synthetic resin by reaction curing, which contains a siloxane / polyoxyalkylene graft copolymer-containing synthetic resin molding aid for improving wettability to a substrate by adding it to a synthetic resin or precursor. A method for producing a synthetic resin molded article, which comprises subjecting a precursor to reaction curing while contacting with a substrate having a releasable surface. 2. The organopolysiloxane chain is a linear organopolysiloxane chain having no siloxane unit (C), and each of the two terminal triorganosiloxane units (D) is a functional group capable of reacting with an isocyanate group. The method of claim 1 having an organic group having a group. 3. An organic group having a functional group capable of reacting with an isocyanate group (However, R ¹⁰ is a divalent hydrocarbon group having 20 or less carbon atoms, R ¹¹
Is an alkylene group having 2 to 8 carbon atoms, k is 0 or 1, and m is 0 or an integer of 1 or more). 4. When the number of diorganopolysiloxane units (A) in the graft copolymer is a and the number of diorganosiloxane units (B) is b, they are 1 ≦ a / b ≦ 2.
The method according to claim 1, which has a relationship of 5. 5. The diorganopolysiloxane unit (B) having a polyoxyalkylene chain, wherein the polyoxyalkylene chain bonded to the silicon atom is CH _{2 d} OC ₂ H _{4 e} OC ₃ H _6
f- OX (where d is an integer of 1 to 4, e is an integer of 1 or more, f is 0 or an integer of 1 or more, X is a hydrogen atom or an alkyl group, and OC ₂ H ₄ units and OC ₃ H ₆ Units may be connected in block or random form)
A polyoxyalkylene chain represented by:
The described method. 6. The method according to claim 1, wherein the synthetic resin is a synthetic resin having a bond formed by a reaction between an isocyanate group and a functional group reactive with the isocyanate group. 7. The method of claim 1, wherein the reactive precursor comprises a mixture of polyol and polyisocyanate. 8. The content of the auxiliaries with respect to the synthetic resin raw material is 0.02.
The method of claim 1, wherein the method is -15% by weight. 9. A diorganosiloxane unit (A) having no polyoxyalkylene chain, a diorganosiloxane unit (B) having a polyoxyalkylene chain, and a trifunctional or tetrafunctional siloxane unit (C) which may optionally be present. ), And at least two terminal triorganosiloxane units (D), at least one of the terminal triorganosiloxane units (D) having in its organic group a functional group capable of reacting with an isocyanate group. A flowable reactive precursor comprising a siloxane / polyoxyalkylene graft copolymer and containing a synthetic resin molding aid is cast onto a smooth base material surface having a releasable surface and is reactively cured. A method for producing a synthetic resin film or sheet having a smooth surface.