JP5164552B2 - (Meth) acrylic mucosa conditioning material flow control silicone coating material kit - Google Patents

Description

The present invention relates to a silicone coating material kit capable of controlling the fluidity (deformability) of a (meth) acrylic dental mucosal preparation that can be deformed in accordance with the movement of the oral mucosa because it has appropriate viscoelasticity. .
More specifically, since it has moderate viscoelasticity and can be deformed according to the movement of the oral mucosa, (meth) acrylic dentistry is used for denture patients who have deformation or inflammation of the oral mucosa in dental treatment. The present invention relates to a silicone coating material kit that can control the deformation performance of a mucosa-adjusting material.

  It has been known that when a denture user has used a denture for a long period of time, the shape of the oral cavity gradually changes due to the absorption of alveolar bone forming the ridge. In such a case, the fit between the denture base and the oral mucosa becomes poor, and the denture becomes unstable. If a denture with a poor fit is used as it is, non-uniform pressure is applied to the mucosa below the denture base, causing ulcers and inflammation in the mucosa and causing pain due to occlusal pressure.

When such incompatibility occurs, it is necessary to restore the compatibility of the denture with the mucous membrane by creating a new denture or lining the denture in use.
However, since the oral mucosa of patients with significant ulcers and inflammation is extremely unstable, wait until the oral mucosa is relatively healthy before making or denying a new denture. It is necessary to ensure good compatibility.

The material used in such a case is a dental mucosa adjusting material. That is, the dental mucosa adjusting material is a therapeutic material used by lining the mucosal surface of the denture in use until the shape and color tone of the mucosa under the denture base are restored to a normal state.
Currently, there are three types of soft materials related to denture bases: denture base fixing glue (so-called denture stabilizer), dental mucosa conditioning materials, and soft lining materials, all of which are used. The purpose, method, period of use, requirements, etc. are different.

  For example, a denture base fixing paste is used for a very short period of time by a patient himself / herself for pain relief. It is limited to temporary use and is not a material intended for treatment. There are powdery, creamy, and seal-like ones, and there are water-soluble and water-insoluble ones. The former increases the viscosity of saliva and expects an increase in adhesion to the mucosal surface of the denture base. The latter water-insoluble one eliminates the gap between the denture base and the mucosal surface and improves the compatibility, and also expects the adsorbing power by the marginal sealing effect. Since the composition has almost no elasticity and a large plastic deformation occurs according to the occlusal pressure every time it is bitten, the period of use of the paste material for fixing a denture base is limited to one day or several days.

  On the other hand, the dental mucosa-adjusting material and the soft lining material are common in that the practitioner is a doctor, but the required physical properties differ greatly depending on the purpose of use. Specifically, as described above, the dental mucosal preparation is used for the treatment of the oral mucosa in the stage before the denture repair. It is a soft polymer material used on the surface of the mucosa under the denture base in order to release the strain and indentation of the mucosa under the denture and to mark (also referred to as an impression) a functional form corresponding to the pressure displacement of each part.

In other words, the material has moderate viscoelasticity and can be deformed according to the movement of the oral mucosa, making it a suitable material for functional impressions. A normal impression is called a static impression, while a normal impression is called a dynamic impression. Because it is an impression that can be obtained through a series of movements, it is said that this is a technology that allows a more natural impression.
For this reason, recently, it is frequently used to take an impression in the oral cavity.

  This mucosa-adjusting material is prepared by mixing powder and liquid, and initially shows a paste with high fluidity, but the liquid penetrates the powder and develops viscoelasticity. While the paste is fluid, it is placed on the mucosal surface of the denture base and inserted into the oral cavity for shaping. As a period of use, it takes 1 week to several weeks until the oral mucosa is restored to a healthy state. For that purpose, it should be flexible and minutely deformable to follow the recovery of the oral mucosa while being held on the mucosal surface without being pushed out between the denture and the mucosal surface during occlusion.

  More specifically, lining ulcers and inflammation of the oral mucosa gradually disappears while relieving pain by restoring the compatibility between the denture and the oral mucosa by lining the mucosal surface of the denture with a poor fit to the mucosal preparation. Wait to do. As the ulcers and inflammation of the oral mucosa gradually disappear, the oral mucosa is gradually restored to its original state over time. There is a need to. This is because if the mucous membrane-adjusting material does not deform as described above, the compatibility will be lost as the oral mucosa is restored, and this will cause re-pain. It is.

  A denture base lining material such as a soft lining material is a material used after the oral mucous membrane ulcer and inflammation have finally disappeared and the oral mucosa has obtained a healthy state as described above (however, ulcers) If there is no irritation or inflammation, use a lining material immediately, usually without a mucosal regulator.) The mucosal preparation is used in the presence of ulcers and inflammation, so it must be a very soft material, but the softness required for such purposes is adequate retention of dentures over long periods of time, dentures From the viewpoint of the feeling of use, it is too soft. In addition, since the oral mucosa after the recovery does not cause any further deformation, the high plasticity of the mucosa-adjusting material may adversely affect the denture retention and feeling of use.

  Therefore, as the denture base lining material, even a soft material such as a soft lining material needs to be slightly harder than the mucosa adjusting material and not to show a large plastic deformation. Furthermore, in the case of a mucous membrane preparation material, the period of use is several days to several weeks, whereas the denture base lining material that will constitute the final repair denture functions for at least six months. Is required to be expressed. Furthermore, as a denture base lining material, its mechanical properties such as tensile strength are much higher than those required for the mucosa-adjusting material.

As described above, all of the above three types of materials are soft materials and are used with dentures backed. However, the classification is clearly different as dental materials because of their intended use and required performance. It is to make.
In particular, as for the mucous membrane adjusting material, although not so high strength as described above is required, high flexibility and plasticity are required, and various compositions have been proposed, but from the viewpoint of ease of use, etc. Many of them are mainly composed of a powder material made of (meth) acrylic polymer powder and a liquid material made of various plasticizers (for example, see Non-Patent Documents 1 and 2 and Patent Documents 1 and 2).
The plasticizer is a component necessary for developing flexibility and plasticity. At present, phthalate plasticizers are mainly used.

  More specifically, as a (meth) acrylic dental mucosa-adjusting material, 4-30 masses of a powder component composed of a (meth) acrylic polymer powder such as polyethyl methacrylate or a copolymer thereof and ethanol are used. A kneading material with a liquid component comprising a phthalate plasticizer containing about% is widely used. The liquid component is often mixed with ethanol in order to improve kneading properties, physical properties after kneading, and the like.

Satoshi Kawaguchi and three others, “Factors affecting the dissolution properties of phthalates from prototype mucosal preparations”, Dental Materials and Instruments, Japan Dental Association, July 2004, Vol. 23, Vol. No. 4, p. 273-278 Masaaki Nakamura, “Toward the development of phthalate-free mucosal preparation” [online], March 2003, Japan Dental Association, [January 12, 2005 search], Internet <URL: http: //eturan.bookpark.ne.jp/jdab/pdf/JDAB-200307-008.pdf> Japanese Patent Laid-Open No. 3-20204 JP-A-2-297358 Japanese Patent No. 3105733 JP 2006-225281 A

As described above, the (meth) acrylic dental mucosa preparation material is used to relieve the pain by relieving the compatibility between the denture and the oral mucosa by lining the mucosal surface of the denture that has been poorly matched, and the oral mucosa As the ulcer and inflammation of the oral mucosa gradually disappear, the form of the oral mucosa recovers to the original state over time, and the morphological changes of the oral mucosa accompany it. Together, it is plastically deformed.
Therefore, the mucosa adjusting material is a very soft material.

As a result, it is too soft from the viewpoint of proper retention of dentures over a long period of time and the feeling of use of dentures, and the oral mucosa after recovery does not cause any further deformation. However, if it continues to be used until after it is restored to a healthy state, an impression cannot be optimally collected, and there is a case where an impression of the oral mucosa is adversely affected.
In addition, after removing the mucous membrane preparation from the oral cavity, if the impression is used immediately, that is, if it is not transferred to a gypsum mold, the shape of the mucosa preparation is changed because it is very soft. It cannot be collected.

  The inventor of the present invention has made extensive research and development in this regard, and as a result, has succeeded in development. That is, the present invention can be achieved by coating the surface of the mucosal conditioning material with a silicone curable composition having a specific composition when the oral mucosa is restored to a healthy state and the form is supposed to be in a proper state. The present inventors have found that a soft and easily deformable mucosa-adjusting material can be taken as an impression without deforming the copied shape, thereby successfully developing the present invention.

Therefore, according to the present invention, the shape taken by the (meth) acrylic dental mucosal preparation that can be deformed in accordance with the movement of the oral mucosa because it has appropriate viscoelasticity is collected in an optimal state. It is an object of the present invention to provide a coating material kit that can control the fluidity (deformability) of a (meth) acrylic dental mucosa-adjusting material.
That is, a coating kit for a (meth) acrylic dental mucosal preparation that can be fixed (held) in a short period of time and taken as an impression without deforming the optimal shape copied by the mucosa preparation. The issue is to provide.

  The inventor of the present invention provides a (meth) acrylic mucosa adjusting material flow control silicone coating material kit for solving the above-mentioned problems, which includes (A) an organic group having a terminal unsaturated bond in the molecule. Silicone comprising an organopolysiloxane having at least two, (B) an organohydrogenpolysiloxane having at least three SiH groups in the molecule, and (C) a hydrosilylation reaction (also referred to as “hydrosilylation reaction”) catalyst. A curable composition, a silicone coating material for flow control of an acrylic mucosa conditioning material having a viscosity at 25 ° C. of 0.1 to 10 Pas of the composition excluding (C), and a reactive function of hydrosilylation reaction (Meth) acrylic polymer modified with a siloxane having a group and an adhesive composed of a volatile organic solvent And it is characterized in Rukoto.

And in this invention, it is preferable to employ | adopt the following aspects.
(1) The cured body of the (meth) acrylic mucosa-adjusting material flow control silicone coating material has a tear strength of 5 N / mm or more.
(2) The (meth) acrylic mucosa-adjusting material flow control silicone coating material further comprises (D) a non-reactive polysiloxane.

  In the present invention, the surface of the (meth) acrylic dental mucosa-adjusting material obtained by copying the shape of the mucous membrane in the oral cavity is previously modified with a siloxane having a reactive functional group for hydrosilylation reaction. (A) Organopolysiloxane having at least two organic groups having terminal unsaturated bonds in the molecule, and (B) SiH groups in the molecule after applying and drying an adhesive comprising a coalescence and a volatile organic solvent. A silicone curable composition comprising an organohydrogenpolysiloxane having at least three and (C) a hydrosilylation reaction catalyst, wherein the composition excluding (C) has a viscosity at 25 ° C. of 0.1 to 0.1. 10 Pas of the acrylic mucosa conditioning material flow control silicone coating material is coated on the surface of the mucosal conditioning material by a simple treatment. It can be achieved excellent effects and advantages can be taken at an optimal state without deforming the shape of the oral mucosa that wood has taken copies in the course of harvesting.

That is, according to the present invention, the surface of the mucosa-adjusting material obtained by copying the optimum shape is covered with the silicone coating material for flow control of the acrylic mucosa-adjusting material, so that the mucosa-adjusting material is very soft and easily deformed. It changes to a property that is difficult to deform in a short time, and thereby, the optimal shape copied can be fixed (held) in a short time without being deformed and collected as an impression.
Therefore, the present invention is excellent in that a dynamic impression obtained through a series of movements in the oral cavity can be collected in an optimum state.
On the other hand, the mucous membrane adjusting material flow control silicone coating material of the present invention is not used, and in the past, it was inevitable that the mucous membrane adjusting material was deformed very softly, but the present invention avoids this for the first time. It is an excellent one that could provide a technology that can be used.

  The present invention provides a (meth) acrylic mucosa adjusting material flow control silicone coating material kit, which comprises (A) an organopolysiloxane having at least two organic groups having terminal unsaturated bonds in the molecule, (B) A silicone curable composition comprising an organohydrogenpolysiloxane having at least 3 SiH groups in the molecule and (C) a hydrosilylation reaction catalyst, wherein 25 of the composition excluding (C) Modified with a (meth) acrylic mucosa conditioning material flow control silicone coating material having a viscosity at 0.1 ° C. of 0.1 to 10 Pas, and a siloxane having a hydrosilylation reactive functional group ( It is comprised from the adhesive agent which consists of a meth) acrylic-type polymer and a volatile organic solvent.

  The greatest feature of the present invention is that the (meth) acrylic-based composition is cured by applying a cured silicone composition having an appropriate viscosity that can be applied onto the (meth) acrylic mucosa-adjusting material. The purpose is to suppress the fluidity (that is, shape deformability) of the mucosa-adjusting material. Silicone is soft and easy to adjust to high strength, and is very rich in its original properties without plastic deformation against the received force. By applying to the surface of the adjusting material, the fluidity of the (meth) acrylic mucosa adjusting material can be effectively suppressed in a small amount. If the effect is simply to suppress the fluidity, it is thought that the effect can be temporarily obtained by applying a harder material to the surface, but there is a difference in hardness from the (meth) acrylic mucosa conditioning material. If it is too much, the applied layer tends to break, which is not practical. Silicone is considered to be extremely excellent in that it has both the above-described softness and property retention.

  On the other hand, silicone has a property that it is extremely difficult to adhere to different materials, and no technology has been found so far for bonding silicone to the (meth) acrylic mucosa-adjusting material. The fluidity control of the (meth) acrylic mucosa-adjusting material to be solved by the present invention can be realized by firmly bonding silicone to the (meth) acrylic mucosal-adjusting material, and is suitable for its realization. Although the appearance of the agent was necessary, the inventors of the present invention developed a compound (Patent Document 3) developed by a researcher belonging to the applicant's company, which is completely different in hardness and properties from the object to be bonded in the patent ( The present inventors have found that it also acts as an adhesive on a meth) acrylic mucosa-adjusting material, and has reached the present invention.

In the present invention,
(1) The cured body of the (meth) acrylic mucosa-adjusting material flow control silicone coating material has a tear strength of 5 N / mm or more.
(2) It is preferable that the (meth) acrylic mucosa adjusting material flow control silicone coating material further comprises (D) a non-reactive polysiloxane.

  The flow-control silicone coating material of the present invention coats the surface of a (meth) acrylic mucosa adjusting material, and the mucosal adjusting material at that time includes a (meth) acrylic polymer powder, a plasticizer, and the like. The liquid material is divided and packaged and stored, and when used, it is prepared as a paste by mixing both materials, and can exhibit high flexibility and plasticity after mixing. Without limitation, various (meth) acrylic polymer powders and liquid materials such as plasticizers can be used.

  The (meth) acrylic polymer powder is not particularly limited, and various methacrylic polymer powders or acrylic polymer powders can be used, and methyl acrylate, methyl methacrylate (abbreviated as MMA). ), Ethyl acrylate, ethyl methacrylate (abbreviated as EMA), propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, or other homopolymers or copolymers thereof.

  Among these polymers, it is preferable to use a homopolymer or copolymer of an ester of methacrylic acid and an alkyl alcohol having 1 to 4 carbon atoms because of its good affinity with the acrylic resin of the denture base. Among them, a copolymer of methyl acrylate and ethyl acrylate, or a homopolymer of methyl methacrylate (MMA) or ethyl methacrylate (EMA) is most preferable.

  The liquid material at that time expresses flexibility and plasticity, and a plasticizer is typically used. As for the plasticizer, it can be blended into the (meth) acrylic polymer powder, and after blending, it can impart high flexibility and plasticity to the (meth) acrylic polymer. Various types of materials can be used without any particular restrictions, such as diethyl phthalate, dibutyl phthalate, dioctyl phthalate, bis (ethylhexyl) phthalate, butyl phthalyl butyl cricolate phthalate, or diethyl sebacate. And sebacate plasticizers such as dibutyl sebacate, dioctyl sebacate, and bis (ethylhexyl) sebacate.

  In addition, for the purpose of controlling kneadability, a solvent is usually used for diluting as necessary, and the solvent is not particularly limited as long as it matches the purpose. In consideration of irritation in the oral cavity, alcohols are suitable, and ethanol, isopropyl alcohol, etc. can be exemplified. preferable.

  The mucosa-adjusting material formed from this (meth) acrylic polymer powder and a plasticizer-containing liquid material loses viscoelasticity and becomes hard in a relatively short period of time, and therefore has a specific glass transition point. Recently, an acrylic mucosa-adjusting material, which is a mixture of a (meth) acrylic polymer and a specific liquid polymer, has been developed. In the present invention, the mucosa-adjusting material can be preferably used. (Patent Document 4).

  The (meth) acrylic mucosa adjusting material flow control silicone coating material kit of the present invention comprises a (meth) acrylic mucosal adjusting material flow control silicone coating material and an adhesive. Acrylic mucosa conditioning material flow control silicone coating material has (A) an organopolysiloxane having at least two organic groups with terminal unsaturated bonds in the molecule, and (B) at least three SiH groups in the molecule. It contains an organohydrogenpolysiloxane and (C) a hydrosilylation reaction catalyst.

These components and the like will be sequentially described in detail below.
The component (A) used in the present invention, which is an organopolysiloxane having at least two organic groups having terminal unsaturated bonds in the molecule (hereinafter abbreviated as unsaturated bond-containing silicone), is component (B) organo It is a main component that becomes a rubber elastic coating layer by crosslinking with hydrogen polysiloxane (hereinafter abbreviated as SiH siloxane).
As long as the unsaturated bond-containing silicone of component (A) is an organopolysiloxane having at least two organic groups having a terminal unsaturated bond in one molecule, the structure of other organic groups is not limited and is linear. It may be a branched chain or a mixture thereof.

  Examples of the organic group having a terminal unsaturated bond include a vinyl group, an allyl group, and a 1-butenyl group, but a vinyl group bonded to a silicon atom is most advantageous because of its ease of synthesis and reactivity. is there. These organic groups having terminal unsaturated bonds may be present at the end or in the middle of the molecular chain of the organosiloxane, or both, but they have excellent reactivity and rubber elasticity after curing. In order to have chemical and physical properties such as mechanical strength of the coating layer, at least one is preferably present at the end.

  Organic groups bonded to silicon atoms other than organic groups having terminal unsaturated bonds include alkyl groups such as methyl, ethyl, propyl, butyl, and octyl groups, aryl groups such as phenyl groups, and chloromethyl groups. Substitued alkyl groups such as 3,3,3-trifluoropropyl group, etc. are exemplified, but among these, the rubber elastic coating layer after curing is sufficient in mechanical strength and coloring resistance, etc. A methyl group is most preferred because it maintains good chemical and physical properties.

A typical unsaturated bond-containing silicone of component (A) used in the present invention is as shown in the following formula (1).

However, in Formula (1), Ph shows a phenyl group.
In addition, the order of bonding of each repeating structural unit in the compound used in the above compound and the examples (Examples and Comparative Test Examples) described later is completely arbitrary, and the number of repeating structural units shown in the structural formula is simply It only shows the average value of the total amount of each structural unit.

  The component (B) SiH siloxane used in the present invention is a component having a function of crosslinking the unsaturated bond-containing silicone to form a rubber elastic coating layer. In order to react with the unsaturated bond-containing silicone to form a crosslinked structure, at least three hydrogen atoms bonded to the silicon atom are required in the molecule. When the number is less than 3, a crosslinked structure is not obtained and a rubber elastic coating layer cannot be obtained.

  Examples of the organic group bonded to a silicon atom other than a hydrogen atom include those similar to the organic group having a terminal unsaturated bond and the organic group having no terminal unsaturated bond in the component (A). The methyl group is most preferred because it is easy to synthesize and retains good chemical and physical properties such as sufficient mechanical strength and color resistance after curing. Such SiH siloxane may be linear, branched or cyclic, or a mixture thereof.

A typical SiH siloxane used in the present invention is as shown in the following formula (2).

However, in Formula (2), Ph shows a phenyl group.
In addition, also in SiH siloxane used in the examples described above and below (Examples of Experiments and Comparative Tests), the bonding order of each repeating structural unit in the molecule is completely arbitrary as in the case of unsaturated bond-containing silicone, and the structure The number of repeating structural units shown in the formula is merely an average value of the total amount of each structural unit.

  The blending amounts of the unsaturated bond-containing silicone and SiH siloxane used in the present invention vary greatly depending on their molecular weights. Usually, however, the unsaturated bond-containing silicone contains one unsaturated bond in the SiH siloxane. What is necessary is just to mix | blend so that it may become the ratio of 0.5 or more, preferably 1-10 hydrogen atoms couple | bonded with the silicon atom. If this ratio is too small, the curability is insufficient, and if it is too large, the resulting rubber elastic coating layer becomes brittle or hydrogen atoms bonded to excess silicon atoms remain, so that the rubber elastic coating layer is stable over time. It tends to decrease.

  Moreover, the hydrogen atom bonded to the silicon atom by the organohydrogenpolysiloxane having at least three hydrogen atoms bonded to the silicon atom in the molecule is 0 for one unsaturated bond in the unsaturated bond-containing silicone. If it is 5 or more, an organohydrogenpolysiloxane containing only two or one hydrogen atom bonded to a silicon atom in the molecule may be added.

The hydrosilylation reaction catalyst, which is the component (C) used in the present invention, is obtained by bonding the component (A) and the component (B) by a hydrosilylation reaction and crosslinking the unsaturated bond-containing silicone. Any material can be used as long as it has a function of forming an elastic coating layer and can be used in a normal hydrosilylation reaction, and a platinum compound is typically used.
Examples thereof include chloroplatinic acid, its alcohol-modified product, platinum vinylsiloxane complex, and the like. In order to improve the storage stability, a material having a small amount of chloro such as a platinum-vinylsiloxane complex is preferable.

  About the compounding quantity of this hydrosilylation reaction catalyst, in the case of a platinum compound which is a typical catalyst, the platinum content is in the range of 0.1 to 1000 ppm with respect to the total weight of the unsaturated bond-containing silicone and SiH siloxane. Just do it. When the blending amount is less than 0.1 ppm, the crosslinking reaction between the unsaturated bond-containing silicone and the SiH siloxane does not proceed sufficiently. When the blending amount is more than 1000 ppm, the rubber elastic coating layer is yellow or severe due to the deposition of platinum black. Problems such as black coloring and difficulty in controlling the crosslinking reaction occur.

  In the present invention, the silicone curable composition needs to have a viscosity at 25 ° C. of 0.1 to 10 Pas of the composition excluding (C). The fluidity is too high, making it difficult to accurately apply to the operator's desired location, and when it exceeds 10 Pas, it becomes a viscous liquid and it is difficult to obtain appropriate applicability with a brush. In order to apply more easily, it is preferably 0.2 to 7 Pas. Furthermore, in the present invention, it is preferable that the (meth) acrylic mucosa adjusting material flow control silicone coating material further comprises (D) a non-reactive polysiloxane, and the viscosity is controlled by containing this. Is easy, and the applicability using a brush is improved, which is preferable.

In the present invention, the tear strength of the cured body of the silicone coating material for flow control of the (meth) acrylic mucosa adjusting material is preferably 5 N / mm or more, and below this, the coating formed by the coating material is broken. In some cases, appropriate fluidity control is difficult to develop.
Furthermore, this strength can be adjusted by using an appropriate filler, and if necessary, appropriate strength can be expressed by limiting the amount of the filler added.

  In the (meth) acrylic mucosa-adjusting material flow control silicone coating material of the present invention, the hydrosilylation reaction proceeds by mixing the component (C) while the components (A) and (B) are mixed. Thus, a cured body is formed. Therefore, it is usually preferable to seal them so that they are not mixed, and it is better for the operator to measure and mix them immediately before use. There is no particular limitation on the sealing method, but it is preferable to make paste-like two packaging in consideration of the ease of measurement and mixing immediately before.

  If it illustrates as a combination of the component in that case, the method divided into the 1st packaging comprised from (A) component and (B) component, and the 2nd packaging comprised from (A) component and (C) component will mention. It is done. In this case, other additive components such as the component (D) may be added to one package or separated into both packages. Also, the packaging container is not particularly limited, but a tube or a cartridge type container that can be separated is preferable from the viewpoint of easy handling.

Next, the adhesive which is another component of the silicone coating material kit for controlling the flow of the (meth) acrylic mucosa-adjusting material of the present invention will be described in detail below.
In the silicone coating material kit for flow control of the (meth) acrylic mucosa adjusting material of the present invention, this adhesive plays a role of adhering the above-mentioned silicone coating material and the (meth) acrylic mucosal adjusting material. That is, it is an important component that enables adhesion of both by applying the adhesive shown below to the surface of the (meth) acrylic mucosa-adjusting material in advance.
The adhesive comprises a (meth) acrylic polymer modified with a siloxane having a reactive functional group for hydrosilylation reaction and a volatile organic solvent, and the acrylic polymer has SiH in the side chain. It is preferable to use a silicone-modified acrylic random copolymer having a polyorganosiloxane having a reactive site.

The silicone-modified (meth) acrylic random copolymer (hereinafter sometimes simply referred to as a random copolymer) is represented by the following general formulas (1) and (2), or (1), (2) and (3). It has a structural unit represented by these.
That is, it is essential that the random copolymer has a structural unit represented by the following general formulas (1) and (2), but it does not contain a structural unit represented by the following general formula (3). Is optional. As will be specifically described later, the random copolymers of the structural formulas (1) to (5) do not contain the structural unit represented by the following general formula (3).

In the formula, R ¹ , R ² and R ¹³ are each a hydrogen atom, a methyl group or an ethyl group, R ³ is an alkyl group having 1 to 13 carbon atoms or an aryl group having 6 to 14 carbon atoms, R ⁴ to R ¹⁰ is an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms, and R ¹¹ and R ¹² are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 14 carbon atoms. R ¹⁴ represents an unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have an ether bond or an ester bond in the main chain, and A may have an ether bond or an ester bond in the main chain. A divalent hydrocarbon group having 2 to 20 carbon atoms, c and d each represent an average number of repeating units, c is an integer of 1 to 100, d is an integer of 0 to 100, and 10 ≦ c + d ≦ 100, 0 ≦ d / c ≦ 10.
Moreover, about the structural ratio of a structural unit (1), a structural unit (2), and a structural unit (3), it is mol%, (1) = 10-99.9, (2) = 90-0.1, (3) = 0 to 89.9, and the weight average molecular weight is 5,000 to 1,000,000.

R ¹ , R ² , and R ¹³ in the general formulas (1), (2), and (3) are each selected from a hydrogen atom, a methyl group, and an ethyl group. From the viewpoint of the ease of synthesis of the random copolymer, particularly the copolymerization reactivity of the raw material monomer (acrylate compound), a hydrogen atom, a methyl group or a mixed system using these in combination is preferred.
Further, R ³ is an alkyl group having 1 to 13 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group or a tridecyl group, a phenyl group, a benzyl group, or a naphthyl group. Selected from aryl groups having 6 to 14 carbon atoms such as a group, and lower alkyl groups such as a methyl group, an ethyl group, and an n-propyl group are most suitable, and one or two selected from these groups A mixed system using the above groups in combination is preferred.

R ^{4 to} R ¹⁰ are each an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, an n-propyl group, and an n-hexyl group, and an alkyl group having 6 to 14 carbon atoms such as a phenyl group, a benzyl group, and a naphthyl group. A methyl group, a phenyl group, or a mixed system using these in combination is preferable because it is selected from aryl groups and is easy to synthesize and obtain a polyorganosiloxane having a SiH reaction point as a synthesis raw material.

R ¹¹ and R ¹² are each a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 14 carbon atoms exemplified by the same kind as R ^{4 to} R ^10, and are raw materials for synthesis. From the viewpoint of the synthesis and availability of organopolysiloxane having SiH reactive sites and the high reactivity of the resulting random copolymer, a hydrogen atom, a methyl group, a phenyl group or a mixed system using these in combination is preferred.
R ¹⁴ is a vinyl group, an allyl group, a 1-butenyl group, a 9-decenyl group, a 2- (2- (2- (2-propenyloxy) ethoxy) ethoxy) ethyl group, or a 2- (3-butenoyloxy) ethyl group. And an unsaturated hydrocarbon group having 2 to 20 carbon atoms which may have an ether bond or an ester bond in the main chain such as an oleyl group.

  A is a C2-C20 divalent hydrocarbon group that may have an ether bond or an ester bond in the main chain, and may have an ether bond or an ester bond for ease of synthesis. A divalent hydrocarbon group of several 3 to 10 is preferable. Specifically, the following hydrocarbon groups are exemplified.

  C and d in the general formula (2) represent the average number of repeating units of the siloxane unit, are integers satisfying 1 ≦ c ≦ 100 and 0 ≦ d ≦ 100, and 10 ≦ c + d ≦ 100, 0 ≦ d / It is selected from the range of c ≦ 10. From the viewpoint of reactivity as an adhesive, it is more preferable to select c so as to have 3 or more SiH groups in one unit of polyorganosiloxane group.

  As for the copolymerization ratio of the structural unit (1), the structural unit (2), and the structural unit (3), the mole% of each structural unit is (1) = 10-99.9 mol%, (2) = 90- It is selected to be 0.1 mol% and the structural unit (3) = 0 to 89.9 mol%. Preferably, (1) = 50 to 99.9 mol%, (2) = 50 to 0.1 mol%, and (3) = 0 to 49.9 mol% are selected. Each structural unit may be composed of not only a single unit but also a plurality of units as long as the structural unit of the category represented by the general formula is used.

  When the proportion of the structural unit (1) in the whole is less than 10 mol%, the molecular weight of the polyorganosiloxane group is decreased when the proportion of (2) in the remaining structural units (2) and (3) is large. However, the proportion of the polyorganosiloxane portion in the total random copolymer is larger than that of the acrylic resin portion, and the adhesion with the (meth) acrylic resin of the mucosa-adjusting material becomes worse, so the adhesive strength may be reduced. is there.

When the proportion of the structural unit (2) is less than 0.1 mol%, the proportion of the polyorganosiloxane portion in the total random copolymer becomes small, and the compatibility with the silicone curable composition becomes poor. Adhesive strength with is not sufficient. Here, the polyorganosiloxane portion refers to an SiO skeleton portion having an organic group, and refers to a portion determined by R ^{4 to} R ¹² , c, and d. Further, the acrylic resin portion refers to a polyacrylate skeleton portion, and is a portion other than the polyorganosiloxane portion of the random copolymer used in the present invention, and R ^{1 to} R ³ , R ¹³ , R ¹⁴ , The portion determined by the number of structural units (1), structural units (2), and structural units (3).

The random copolymer in this adhesive has a weight average molecular weight of 5,000 to 1,000,000. Copolymerization of c, d, structural unit (1), structural unit (2), and structural unit (3) is within this range. Ratio, and their total polymerization number.
Furthermore, the ratio between the molecular weight of the polyorganosiloxane portion and the molecular weight of the acrylic resin portion is 1: 0 because of compatibility with the (meth) acrylic resin and the silicone rubber portion, reactivity, and ease of synthesis. It is preferable to select a combination such that.

In the silicone-modified (meth) acrylic random copolymer that is an active ingredient in the adhesive used in the present invention, among the structural units represented by the general formulas (1), (2), and (3), R ^1, R ^2, as R ¹³ is selected from hydrogen or methyl group, the methyl group as R ^3, an alkyl group such as ethyl group, a methyl group as R ⁴ to R ^12, as R ¹⁴ Is a reactive residue of A, A is a divalent alkylene group such as a propylene group, butylene group, decylene group, etc., c and d are integers satisfying 10 ≦ c + d ≦ 100 and 0 ≦ d / c ≦ 10 Yes, selected from the range of 1 ≦ c ≦ 100 and 0 ≦ d ≦ 100.

The structural ratio of the structural unit (1), the structural unit (2), and the structural unit (3) is (1) = 50 to 99.9 mol%, (2) = 50 to 0.1 mol%, (3 ) = 0 to 49.9 mol%. Moreover, those having a weight average molecular weight of 5,000 to 500,000 are preferred for reasons such as easy availability of synthetic raw materials, ease of synthesis, and strong adhesiveness based on the excellent reactivity of the resulting random copolymer.
Since it is as above-mentioned, inclusion of the structural unit represented by General formula (3) in a random copolymer is arbitrary, and does not need to be contained.

Specific examples of the silicone-modified (meth) acrylic random copolymer, which is an active ingredient in the adhesive used in the present invention, are shown in terms of the structure of the structural unit and the average number of repeating units. 1) thru | or (9) etc. are mentioned.
Of these structural formulas, the structural formulas (1) to (8) show the structures of two types of random copolymers, and only the structural formula (9) is a single random copolymer. That is, a random copolymer represented by (A) having a structural unit shown before the symbol “;”, and a random copolymer represented by (B) having a structural unit shown after the symbol “;” Are different and are shown in one structural formula.

In each of the structural formulas, the structural units represented by the general formula (1), the general formula (2), and the general formula (3) are described in that order. For example, in the structural formula (1), in the upper formula (A), the front structural unit is the structural unit represented by the general formula (1), and the rear structural unit is represented by the general formula (2). Represents a structural unit.
As described above, the random copolymers of the structural formulas (1) to (5) do not include the structural unit represented by the general formula (3), and are represented by the general formula (3). The random copolymer containing the structural unit is a random copolymer of the structural formulas (6) to (9).

  In the structural formulas (1) to (9), Ph represents a phenyl group. The bonding order of the structural units in the random copolymer and the siloxane units in the polyorganosiloxane portion in the adhesive used in the present invention used in the random copolymer and the examples and comparative examples described later is completely arbitrary. The number of repeating units shown in the structural formula merely shows the average total amount of each structural unit and each siloxane unit.

The production method of the silicone-modified (meth) acrylic random copolymer used in the adhesive in the present invention is not particularly limited, and a typical method thereof will be specifically described below.
That is, the random copolymer is produced as shown below using raw materials represented by the following general formulas (4) to (7).

一般式（４）で表されるアクリレート化合物（但し、式中Ｒ¹、Ｒ³は一般式（１）と同一定義を有す。）

Acrylate compound represented by general formula (4) (wherein R ¹ and R ³ have the same definition as in general formula (1)).

一般式（５）で表される末端不飽和結合含有アクリレート化合物（但し、式中Ｒ² は一般式（２）と同一定義を有し、Ａ’は単結合、即ちＡ’の左の酸素原子と右の炭素原子が直接結合している、あるいは主鎖にエーテル結合もしくはエステル結合を有してもよい炭素数１〜１８の２価の炭化水素基を表す。）

A terminal unsaturated bond-containing acrylate compound represented by the general formula (5) (wherein R ² has the same definition as in the general formula (2), A ′ is a single bond, ie, an oxygen atom on the left of A ′) And the right carbon atom is directly bonded, or represents a C1-C18 divalent hydrocarbon group which may have an ether bond or an ester bond in the main chain.)

一般式（６）で表される不飽和結合含有アクリレート化合物（但し、式中Ｒ¹³、Ｒ¹⁴は一般式（３）と同一定義を有す。）

Unsaturated bond-containing acrylate compound represented by general formula (6) (wherein R ¹³ and R ¹⁴ have the same definition as in general formula (3)).

一般式（７）で表されるハイドロジェンシリコーン化合物（但し、式中Ｒ⁴ 〜Ｒ¹²、ｃ、ｄは一般式（２）と同一定義を有す。）

Hydrogen silicone compound represented by general formula (7) (wherein R ^{4 to} R ¹² , c and d have the same definition as in general formula (2)).

The synthesis method using the production raw materials of the general formulas (4) to (7) is specifically shown as follows.
That is, the (meth) acrylate compound represented by the general formula (4), the terminal unsaturated bond-containing (meth) acrylate compound represented by the general formula (5), and the general formula (6) as necessary. It is synthesized by adding a hydrogen silicone compound represented by the general formula (7) to a copolymer of an unsaturated bond-containing (meth) acrylate compound by a hydrosilylation reaction using a platinum catalyst.

When the above-described synthesis method is used, R ¹⁴ in the structural unit (3) represented by the structural formula (3) is the case where the unsaturated bond-containing (meth) acrylate compound represented by the general formula (6) is not used. The unreacted residue in the terminal unsaturated bond-containing (meth) acrylate compound of the general formula (5) that is the synthetic raw material, that is, -A′-CH═CH ₂ , and the unsaturated bond of the general formula (6) When a (meth) acrylate compound is used, R ¹⁴ in the unsaturated bond-containing (meth) acrylate compound of the general formula (6) or R in the unsaturated bond-containing (meth) acrylate compound of the general formula (6) ¹⁴ and a mixture of unreacted residues in the terminal unsaturated bond-containing (meth) acrylate compound of the general formula (5).

These syntheses, that is, a (meth) acrylate compound, a terminal unsaturated bond-containing (meth) acrylate compound and, if necessary, a copolymerization reaction of an unsaturated bond-containing (meth) acrylate compound, this copolymer and a hydrogen silicone compound Any of the hydrosilylation reactions can be carried out by known methods.
For example, for the synthesis of a copolymer, a (meth) acrylate compound, a terminal unsaturated bond-containing acrylate compound, an unsaturated bond-containing (meth) acrylate compound and, for example, benzoyl peroxide, azobisisobutyronitrile, etc. A solution polymerization in which the radical polymerization initiator is heated and polymerized in a solvent such as toluene, methylene chloride, chloroform or the like, or a suspension polymerization in which a surfactant is polymerized in water is preferably used.

For hydrosilylation reactions, the amount of terminal double bonds of the (meth) acrylic polymer having a double bond at the end of the side chain and the (meth) acrylic polymer having a double bond at the end of the side chain is as described above. An amount of hydrogen silicone compound that is in a large molar excess with respect to the hydrogen silicone compound, an inert substance that simultaneously dissolves the hydrogen silicone compound and the (meth) acrylic polymer having a double bond at the side chain end, such as toluene, A silicone-modified (meth) acrylic random copolymer of the present invention can be obtained by charging a reaction vessel with a solvent such as methylene chloride and a platinum catalyst, and heating and stirring while bubbling nitrogen to remove the influence of moisture. .
In addition to this, a hydrogen silicone compound having a (meth) acryloxyalkyl group in the side chain and the (meth) acrylate compound of the general formula (4) and, if necessary, the general formula (6) may be used together. The random copolymer of the present invention can also be obtained by polymerization.

As apparent from the above synthesis method, the total molecular weight of the silicone-modified (meth) acrylic random copolymer of the present invention, the molecular weight of the poly (meth) acrylate moiety, the structural unit (1), the structural unit (2), and Resin constituents such as the copolymerization ratio of the structural unit (3), the molecular weight of the polyorganosiloxane moiety, the constituent unit ratio (c / d) of each siloxane unit, the types of organic groups R ^{1 to} R ¹⁴ , A, and combinations thereof All of these can be arbitrarily selected.

That is, the molecular weight of the poly (meth) acrylate moiety can be controlled by known methods such as the amount of the polymerization initiation catalyst during the copolymerization reaction, the addition of a chain transfer agent, and the structural unit (1), structural unit (2), structure The copolymerization ratio of the unit (3) depends on the charge ratio of the corresponding monomer and the reaction rate of the addition reaction of the hydrogen silicone compound, that is, depending on the reaction conditions, and the organic groups R ^{1 to} R ³ , R ¹³ , R ¹⁴ , A The type and combination can be controlled by using a monomer having a required organic group in a required mixing ratio and controlling the reaction rate of the addition reaction of the hydrogen silicone compound, that is, the reaction conditions. Moreover, also about the polyorganosiloxane part, the molecular weight, the structural unit ratio (c / d) of each siloxane unit, the kind and combination of organic group R < ⁴ > -R < ¹² > can be controlled arbitrarily.

The silicone-modified (meth) acrylic random copolymer thus obtained is generally a white powdery solid.
This silicone-modified (meth) acrylic random copolymer is a compound developed by a researcher belonging to the applicant company (Patent Document 3), and its performance as an adhesive is truly amazing.
In order to use the above silicone-modified (meth) acrylic random copolymer as an adhesive, the copolymer is moderately concentrated in a soluble organic solvent such as toluene, methylene chloride, chloroform, tetrahydrofuran, ethyl acetate, acetone, and the like. The adhesive is preferably dissolved to about 0.1 to 20% by weight.

Although there is no restriction | limiting in the usage method of the silicone coating material kit for (meth) acrylic-type mucous membrane regulator flow control in this invention, A typical usage method is explained in full detail below.
After washing the (meth) acrylic mucosa conditioning material used in the patient's mouth with running water and wiping away the water, apply the (meth) acrylic mucosal conditioning material flow control silicone coating material of the present invention to the part Apply the adhesive that makes up this kit with a brush. At this time, there is no clear limitation on the amount of the adhesive applied, but it is preferable to apply the adhesive uniformly to such an extent that the surface to be bonded can be seen wet with the adhesive.

After applying the adhesive, leave the organic solvent remaining on the surface for several tens of seconds or with air, and then weigh the (meth) acrylic mucosa conditioning material flow control silicone coating material previously measured on it. Knead and apply. Although there is no clear limitation on the amount applied, it is about 0.1 to 1.0 mm in order to effectively suppress the fluidity of the surface of the (meth) acrylic mucosa-adjusting material and not impair the obtained impression accuracy. It is preferable to keep the thickness. After the applied (meth) acrylic mucosa adjusting material flow control silicone coating material is cured, it can be buried in gypsum or the like to take an impression.

In order to describe the present invention more specifically, examples (examples of experimental tests and comparative test examples) will be shown below. However, the present invention is specified by the description of the scope of claims. It is not limited at all.
The materials used in each test example and comparative test example are as follows.
In each of the test examples, components (A) to (F) are used, and they are as follows.

Component (A) [unsaturated organopolysiloxane]
Several types of this component (A) are used, and they are summarized in Table 1.

Component (B) [organohydrogenpolysiloxane]
Several types of this component (B) are also used and are summarized in Table 2.

Component (C) and component (D) are as follows.
Component (C) [hydrosilylation reaction (also referred to as “hydrosilylation reaction”) catalyst substance]: platinum-divinyldisiloxane complex Component (D) [non-reactive siloxane]: polydimethylsiloxane “TSE451-10” (Toshiba Silicone) Made)
In addition to these, further fillers were used as follows.
Fumed silica "Leoro Seal ZD-30ST" (Made by Tokuyama)

The raw materials used for preparing the adhesive are as follows.
(A) Organic solvent Ethyl acetate (Wako Pure Chemicals, special grade)
Acetone (Wako Pure Chemicals, special grade)
Diethyl ether (Wako Pure Chemicals, special grade: abbreviated as ether)
(B) Reactive siloxane modified (meth) acrylic polymer

Regarding the reactive siloxane-modified (meth) acrylic polymer (b), a copolymer was used in all the examples, and these are shown in the following chemical formulas (1) to (5). It is.
In addition, a method for synthesizing these copolymers (hereinafter, these copolymers are abbreviated as copolymers (1) to (5) in order) will be sequentially shown below.

Synthesis method of copolymer (1) 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.26 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask and heated to 70 ° C. while bubbling nitrogen. As a result, a copolymer (weight average molecular weight of 120,000) having a copolymerization ratio of methyl methacrylate and allyl methacrylate of 50: 1 (molar ratio) was obtained.
The flask was charged with 27.7 g of a hydrogen siloxane compound (DMS-M20H20) shown in Table 1, 300 ml of toluene, and 0.33 g of a platinum / divinylsiloxane complex solution adjusted to 1000 ppm of platinum, and heated to 80 ° C. while bubbling nitrogen. Stir.

  Next, a solution prepared by dissolving 5 g of a copolymer (weight average molecular weight 120,000) of 50: 1 (molar ratio) of methyl methacrylate and allyl methacrylate synthesized in the above method in 100 ml of toluene is dropped over 1 hour. Then, after completion of dropping, the mixture was further heated and stirred for 6 hours, toluene was removed under reduced pressure, excess DMS-M20H20 was washed with a methanol / ethanol mixed solvent, and then filtered and dried to obtain a copolymer (1). . The weight average molecular weight of the obtained polymer was 180,000 as a polystyrene standard.

Method of synthesizing copolymer (2) 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.40 g of azobisisobutyronitrile, and 30 ml of toluene were placed in a flask, and the mixture was heated and stirred at 70 ° C. while bubbling nitrogen. A copolymer (weight average molecular weight 80000) having a copolymerization ratio of 50 to 1 (molar ratio) of allyl methacrylate was obtained.
Using the hydrogen siloxane compound DMS-M10H10P10 shown in Table 1 and a copolymer (weight average molecular weight 80000) having a copolymerization ratio of 50: 1 (molar ratio) of methyl methacrylate and allyl methacrylate synthesized by the above method. Synthesis was performed in the same manner as the synthesis of the polymer (1) to obtain a copolymer (2).

Synthesis method of copolymer (3) 25 g of methyl methacrylate, 1.30 g of methacrylic acid triethylene glycol monoallyl ether ester, 0.31 g of azobisisobutyronitrile and 30 ml of toluene were placed in a flask, and 70 ° C. while bubbling nitrogen. The mixture was heated and stirred to obtain a copolymer (weight average molecular weight 110000) having a copolymerization ratio of methyl methacrylate and triethylene glycol monoallyl ether ester of 50: 1 (molar ratio).
Copolymer (weight average) having a copolymerization ratio of 50 to 1 (molar ratio) between the hydrogen siloxane compound DMS-M20H20 shown in Table 1 and methyl methacrylate synthesized by the above-mentioned method and triethylene glycol monoallyl ether methacrylate. Using a molecular weight of 110000), the synthesis was performed in the same manner as the synthesis of the copolymer (1) to obtain a copolymer (3).

Synthesis Method of Copolymer (4) 25 g of methyl methacrylate, 1.1 g of allyl methacrylate, 0.57 g of azobisisobutyronitrile and 30 ml of toluene are placed in a flask, and heated to 70 ° C. with nitrogen bubbling and stirred to 70 ° C. And a copolymer (weight average molecular weight 60000) of 57: 2 (molar ratio) copolymerization ratio of allyl methacrylate.
Copolymer using hydrogen siloxane compound DMS-M20H20 and copolymer (weight average molecular weight 80,000) having a copolymerization ratio of methyl methacrylate and allyl methacrylate of 57: 2 (molar ratio) synthesized by the above method. Synthesis was performed in the same manner as in the synthesis of (1) to obtain a copolymer (4).

Synthesis Method of Copolymer (5) Put 25 g of methyl methacrylate, 0.63 g of allyl methacrylate, 0.31 g of azobisisobutyronitrile, and 30 ml of toluene into a flask and heat and stir to 70 ° C. while bubbling nitrogen. A copolymer (weight average molecular weight 100000) having a copolymerization ratio of 50 to 1 (molar ratio) of styrene and allyl methacrylate was obtained.
Using the hydrogen siloxane compound DHS-M20H20 shown in Table 1 and a copolymer (weight average molecular weight 100000) having a copolymerization ratio of 50: 1 (molar ratio) of methyl methacrylate and allyl methacrylate synthesized by the above method. The copolymer (5) was obtained by synthesizing by the same method as the synthesis of the polymer (1).

The hydrogen siloxane compounds used in the synthesis methods of these copolymers (1) to (5) are shown together in Table 3.

Using these copolymers, adhesives shown in Table 4 below were prepared. In the preparation, the above copolymer was blended with the organic solvent described in Table 4 in the blending ratio shown in the same table, and stirred and mixed until uniform to obtain a desired adhesive. .

The (meth) acrylic mucosa-adjusting material to be treated by the (meth) acrylic mucosa-adjusting material flow control silicone coating material kit of the present invention was as follows.
"Tissue care" (manufactured by Tokuyama Dental)
In the examples (namely, the test examples and comparative test examples), the (meth) acrylic mucosa adjusting material flow control silicone coating material was evaluated by the following evaluation method.
That is, the (meth) acrylic mucosa adjusting material flow control silicone coating material was evaluated by viscosity, coating properties, film thickness, adhesiveness, pressure resistance, and tear strength. The evaluation methods are as follows.

(1) Viscosity After thoroughly kneading the other components except the component (C) in a mortar, the viscosity of the composition subjected to defoaming treatment under reduced pressure was measured using an E-type viscometer.

(2) Applicability The applicability when the composition mixed immediately before was applied to the surface of the acrylic mucosa-adjusting material using a dental brush ("Brush Brush No. 5" manufactured by Tokuyama Dental Co., Ltd.) Rated by stage.
A; It is possible to apply without feeling resistance in particular, and it spreads quickly and uniformly after application, and the back of the brush does not remain on the application surface.
B; Although a slight resistance is felt to the brush at the time of application, it can be uniformly applied, and spreads quickly and evenly after application, and the back of the brush does not remain on the application surface.
C: When applying, the brush feels resistance or does not feel resistance, but the brush mark remains on the coated surface and does not disappear.
D: Although it is possible to apply without feeling resistance in particular, it spreads too much during application and a uniform application surface cannot be obtained.

(3) Film thickness The composition mixed immediately before is applied to the surface of a (meth) acrylic mucosa conditioning material having a size of 20 × 20 × 2 mm using a dental brush (“brush brush No. 5” manufactured by Tokuyama Dental). After coating, it was allowed to stand at 37 ° C. for 5 minutes. The thickness of the cured body was measured, and the thickness of the applied film was determined.
The film thickness is preferably 100 μm or less so as not to impair the impression.

(4) Adhesiveness The composition mixed immediately before is applied to the surface of a (meth) acrylic mucosa conditioning material measuring 20 × 20 × 2 mm using a dental brush (“Brush Brush No. 5” manufactured by Tokuyama Dental). And then allowed to stand at 37 ° C. for 5 minutes. The surface and interface were rubbed with a metal spatula, and whether or not the coating layer was adhered to the (meth) acrylic mucosa-adjusting material was evaluated in the following three stages.
A: Even if it is rubbed with a spatula, it is not easily peeled off, and if it is forcibly peeled off, the acrylic mucosa conditioning material layer on the lower surface is destroyed.
B: Even if it is rubbed with a spatula, it is not easily peeled off, but if it is forcibly peeled, a part is peeled off. C: When it is rubbed with a spatula, it is easily peeled off.

(5) Pressure resistance The composition mixed immediately before is all applied to the surface of a (meth) acrylic mucosa conditioning material measuring 20 × 20 × 2 mm using a dental brush (“brush brush No. 5” manufactured by Tokuyama Dental). After coating on the surface, the plate was allowed to stand at 37 ° C. for 5 minutes.
Using a repeated load tester ("Servo Pulser" manufactured by Shimadzu) on the sample after standing, a repeated load was applied under the following conditions, and the change in thickness before and after the test was evaluated by the thickness recovery rate.
Restoration rate (%) = Thickness after test (mm) / Thickness before test (mm) × 100
Repeated load test conditions ・ Load: 10kg
・ Number of integration: 1500 times ・ Frequency: 1.0 Hz
Test environment: 37 ° C. water In addition, the pressure resistance is desirably 80% or more so that the impression obtained can be recorded on gypsum and the like.

(6) Tear strength Tear strength was measured according to JIS K6252. In addition, the used test piece was produced from the type | mold without a 90 degreeC notch.

[Execution test example 1]
The adhesive shown in Table 5 was applied to the (meth) acrylic mucosa-adjusting material that had been immersed in 37 ° C. for 24 hours, and was sufficiently volatilized. On the surface of the (meth) acrylic mucosa-adjusting material subjected to the above treatment, the pastes A and B for the silicone coating material composition prepared with the composition shown in Table 5 were thoroughly kneaded for about 30 seconds on kneaded paper. It applied and various evaluation was performed. Separately, the tear strength of the cured silicone coating material was evaluated. The results are shown in Table 7.

  As shown in Table 7, the composition excluding the hydrosilylation reaction catalyst (C) had a viscosity at 25 ° C. of 0.4 Pas, and the coating property on the surface of the (meth) acrylic mucosa preparation was good. It was. The film thickness at that time was found to be a thickness that does not hinder the impression obtained at 50 μm. In addition, the adhesion with the (meth) acrylic mucosa conditioning material is also good, the pressure resistance is a result of a restoration rate of 95%, and the tear strength of the cured silicone coating material is 7.5 N / mm. Indicated.

[Execution Test Examples 2 to 21]
The silicone coating material composition pastes A and B prepared with the compositions shown in Table 5 and Table 6 were prepared and evaluated in the same manner as in Test Example 1. The results are shown in Table 7 together with Test Example 1.
As shown in Table 7, the viscosity at 25 ° C. of the composition excluding the hydrosilylation reaction catalyst (C) was lower than 10 Pas, and the coating property on the surface of the (meth) acrylic mucosa conditioning material was good. . It was found that the film thickness at that time was a thickness that did not hinder the impression obtained. Moreover, the adhesiveness with the (meth) acrylic mucosa-adjusting material was also good, and both the pressure resistance and the tear strength of the cured silicone coating material showed good results.

[Comparative Test Example 1]
Silicone coating material composition pastes A and B prepared with the compositions shown in Table 6 were prepared and evaluated in the same manner as in Test Example 1. The results are shown in Table 7.
As shown in Table 7, since the viscosity at 25 ° C. of the composition excluding the hydrosilylation reaction catalyst (C) is extremely low at 0.07 Pas, uniform application to the surface of the (meth) acrylic mucosa-adjusting material is possible. The film thickness could not be measured accurately. The protrusion of the (meth) acrylic mucosa-adjusting material was partially confirmed, and the pressure resistance was 45%.

[Comparative Test Example 2]
Silicone coating material composition pastes A and B prepared with the compositions shown in Table 6 were prepared and evaluated in the same manner as in Test Example 1. The results are shown in Table 7.
As shown in Table 7, since the viscosity at 25 ° C. of the composition excluding the hydrosilylation reaction catalyst (C) is extremely high at 140 Pas, it cannot be uniformly applied to the surface of the (meth) acrylic mucosa conditioning material. It was. Further, although the accurate film thickness could not be measured, the average film thickness was 284 μm, resulting in a very thick film.

[Comparative Test Example 3]
Evaluations were made in the same manner as in Test Example 1 except that the pastes A and B for the silicone coating material composition prepared with the compositions shown in Table 6 were prepared and samples were prepared without using the adhesive. The results are shown in Table 7.
As shown in Table 7, the prepared silicone coating material did not adhere to the (meth) acrylic mucosa-adjusting material at all, and the pressure resistance was 5%.

[Comparative Test Example 4]
Evaluation was performed in the same manner as in Test Example 1 without using the silicone coating material composition and the adhesive. The results are shown in Table 7.
As shown in Table 7, in the absence of the silicone coating material, the deformation of the (meth) acrylic mucosa adjusting material was large and the pressure resistance was 5%.

Claims (3)

  (A) an organopolysiloxane having at least two organic groups having terminal unsaturated bonds in the molecule, (B) an organohydrogenpolysiloxane having at least three SiH groups in the molecule, and (C) a hydrosilylation reaction. A silicone curable composition comprising a catalyst, wherein the composition excluding (C) has a viscosity at 25 ° C. of 0.1 to 10 Pas (meth) acrylic mucosal regulator flow control silicone coating material, (Meth) acrylic mucosa preparation characterized by comprising a (meth) acrylic polymer modified with siloxane having a reactive functional group for hydrosilylation reaction and an adhesive comprising a volatile organic solvent Silicone coating material kit for material flow control.   2. The (meth) acrylic mucosa-adjusting material flow control silicone coating material has a tear strength of 5 N / mm or more, and the (meth) acrylic mucosa-adjusting material flow control silicone coat according to claim 1 Material kit.   The (meth) acrylic mucosa-adjusting material flow control silicone coating material further comprises (D) a non-reactive polysiloxane, The (meth) acrylic mucosa-adjusting material flow control according to claim 1 or 2, Silicone coating material kit.