Surface treatment agent, surface treatment agent kit, surface-modified molded article, and method for producing surface-modified molded article

Abstract

The present invention provides a surface treatment agent containing a prescribed hydrosilane compound and a borane catalyst. By contacting the surface treatment agent with a molded article containing a polyolefin having a polar group on the surface in a solvent containing 10% by volume or more of a hydrocarbon solvent having a total carbon atom number of 5 or more having at least one substituent, a dehydrogenative condensation reaction between the molded article and the hydrosilane compound is performed, and thus the molded article can be modified.

Description

Technical Field

[0001] This invention relates to surface treatment agents, surface treatment agent kits, surface-modified molded articles, and methods for manufacturing surface-modified molded articles. Background Technology

[0002] By modifying the surface of a molded article with specific molecular structures, it is possible to endow the article with desired functions or enhance its existing functions. This functionalization or enhancement can be based on the properties of the molecular structures introduced through surface modification and the morphology of the molded article.

[0003] In recent years, various surface treatment methods for substrates have been developed (see, for example, Patent Documents 1 and 2). Specifically, Patent Document 1 describes a technique in which a substrate with polar groups on its surface is contacted with a hydrosilane compound containing a desired molecular structure in the presence of a borane catalyst, thereby causing a dehydrogenation condensation reaction between the substrate and the hydrosilane compound to obtain a substrate with a desired molecular structure modified on its surface. Furthermore, Patent Document 2 describes a surface modification method in which a surface-modifying compound is contacted with the surface while being irradiated with light of a specific wavelength in the presence of a photoinitiator.

[0004] Prior technology documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2015 / 136913;

[0007] Patent Document 2: International Publication No. 2018 / 029065. Summary of the Invention

[0008] The problem the invention aims to solve

[0009] In recent years, there has been a demand for surface modification of molded articles containing polyolefins in order to impart or enhance desired properties. However, even with the direct application of existing surface modification methods, it is difficult to perform surface modification without eroding the surface of the molded article containing polyolefins.

[0010] Therefore, the object of the present invention is to provide a surface treatment agent that can perform surface modification without excessively eroding the surface of molded articles containing polyolefins.

[0011] Furthermore, the present invention aims to provide a surface treatment agent kit that can perform surface modification without excessively eroding the surface of molded articles containing polyolefins.

[0012] Therefore, the object of the present invention is to provide a surface-modified molded article comprising a polyolefin.

[0013] Furthermore, the present invention aims to provide a method for manufacturing a surface-modified molded article, which enables surface modification without excessively eroding the surface of the molded article containing polyolefins.

[0014] Solution for solving the problem

[0015] The inventors conducted in-depth research to solve the aforementioned problems. They then discovered that by contacting a surface treatment agent containing a prescribed hydrosilane compound and a borane catalyst with a polyolefin-containing molded article having polar groups on its surface in a solvent containing 10% by volume or more of a hydrocarbon solvent having at least one substituent, a dehydrogenation condensation reaction occurs between the molded article and the hydrosilane compound, thereby enabling surface modification without excessively corroding the surface of the polyolefin-containing molded article. This invention thus completes the present invention.

[0016] That is, the object of the present invention is to advantageously solve the above-mentioned problems. [1] The surface treatment agent of the present invention is characterized in that it contains a hydrosilane compound and a borane catalyst, wherein the hydrosilane compound has a Si-H group bonded to a silicon atom in molecular structure A, and the surface treatment agent is contacted with a molded article containing a polyolefin having polar groups on its surface in a solvent containing 10% by volume or more of a hydrocarbon solvent having at least one substituent and a total carbon number of 5 or more, thereby causing a dehydrogenation condensation reaction between the molded article and the hydrosilane compound, thereby modifying the molded article by the molecular structure A. Thus, by contacting a surface treatment agent containing a specified hydrosilane compound and a borane catalyst with a molded article containing polar groups on its surface in a solvent containing 10% by volume or more of a hydrocarbon solvent having at least one substituent and a total carbon number of 5 or more, surface modification can be performed without excessively corroding the surface of the molded article containing the polyolefin.

[0017] [2] The surface treatment agent described above [1] is preferably used in a solvent containing 10% by volume or more of a hydrocarbon solvent having a total carbon number of 5 or more and having at least one methyl group as a substituent. By using the surface treatment agent in this particular hydrocarbon solvent, surface modification can be performed efficiently without excessively corroding the surface of the molded article containing polyolefin.

[0018] [3] Furthermore, the surface treatment agents described in [1] or [2] above can be used on molded articles containing cyclic olefin (co)polymers as polyolefins. According to the surface treatment agents described in [1] or [2] above, surface modification can be performed efficiently without excessively eroding the surface of molded articles containing cyclic olefin (co)polymers. In addition, in this specification, "cyclic olefin (co)polymer" refers to homopolymers of cyclic olefins and copolymers of cyclic olefin units with other copolymerizable units.

[0019] [4] Furthermore, the object of the present invention is to advantageously solve the above-mentioned problems. The surface treatment agent kit of the present invention is characterized by comprising an agent A containing a hydrosilane compound and an agent B containing a borane catalyst, wherein the hydrosilane compound has a Si-H group bonded to a silicon atom in molecular structure A, the agent A and the agent B each contain at least one organic solvent, which may be the same or different, wherein at least 10% by volume of the total organic solvent contained in the agent A and the agent B is a hydrocarbon solvent having at least one substituent and having a total carbon number of 5 or more, and by contacting the agent A and the agent B with a molded article containing a polyolefin having polar groups on its surface, a dehydrogenation condensation reaction is carried out between the molded article and the hydrosilane compound, thereby modifying the surface of the molded article through molecular structure A. According to this surface treatment agent kit, surface modification can be performed without excessively corroding the surface of a molded article containing a polyolefin.

[0020] [5] In the above-mentioned [4] surface treatment agent kit, preferably, at least one substituent of the hydrocarbon solvent is methyl. According to the surface treatment agent kit containing this specific hydrocarbon solvent, surface modification can be performed efficiently without excessively eroding the surface of molded articles containing polyolefins.

[0021] [6] Furthermore, the surface treatment agent kits described in [4] or [5] above can be used for molded articles containing cyclic olefin (co)polymers as polyolefins. According to the surface treatment agent kits described in [4] or [5] above, surface modification can be performed efficiently without excessively eroding the surface of molded articles containing cyclic olefin (co)polymers.

[0022] [7] Furthermore, the object of the present invention is to advantageously solve the above-mentioned problems, and the surface-modified molded article of the present invention is characterized in that it contains a polyolefin having the following molecular structure A on its surface.

[0023] [Chemical Formula 1]

[0024]

[0025] [wherein, R] 1 R 2 Y 1 Y 2 Y 3 Y 4 Each of the following independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 30 carbon atoms, and -OR 4 R 4 This refers to a straight-chain or branched alkyl group having 1 to 30 carbon atoms. In this case, R... 1 R 2 R4 Y 1 Y 2 Y 3 Y 4 Alkyl groups with 1 to 30 carbon atoms, whether straight-chain or branched, can have fluorine atoms as substituents, and multiple carbon atoms can be replaced by oxygen atoms. However, there are no cases where oxygen atoms are substituted in more than two consecutive forms. 1 X 2 X 3 Each can be used independently to represent -O- or a single bond, where l represents an integer greater than 1 and less than 300, and n and m represent integers greater than 0 and less than 300. Where R... 1 R 2 Y 1 Y 2 Y 3 Y 4 At least one of them is not a hydrogen atom.

[0026] The surface-modified molded article has a good surface condition and contains polyolefins, making it suitable for a variety of applications.

[0027] [8] The surface-modified molded article of [7] above is used for medical purposes, and the shape of the molded article can be a petri dish, tube, well plate, syringe or pipette tip.

[0028] [9] Furthermore, in the surface-modified molded articles described in [7] or [8] above, the polyolefin is preferably a cyclic olefin (co)polymer. This surface-modified molded article contains a cyclic olefin (co)polymer, and therefore possesses the desirable properties resulting therefrom.

[0029]

[10] Furthermore, the object of the present invention is to advantageously solve the above-mentioned problems. The method for manufacturing a surface-modified molded article of the present invention is characterized by comprising the following steps: in a solvent containing 10% by volume or more of a hydrocarbon solvent having at least one substituent and a total carbon number of 5 or more, in the presence of a borane catalyst, a molded article formed of a polyolefin having polar groups on its surface is brought into contact with a hydrosilane compound having Si-H groups having hydrogen atoms bonded to silicon atoms of molecular structure A, thereby causing a dehydrogenation condensation reaction between the molded article and the hydrosilane compound, thereby forming the molded article whose surface is modified by the molecular structure A. According to this method for manufacturing a surface-modified molded article, surface modification can be performed without excessively eroding the surface of the molded article containing polyolefin.

[0030]

[11] In the manufacturing method of the surface-modified molded article described in

[10] above, it is preferable that the polar group includes both or either a hydroxyl group or a carbonyl group. By using a molded article formed of polyolefin having both or either a hydroxyl group or a carbonyl group present on its surface as the target, surface modification can be carried out efficiently.

[0031]

[12] Furthermore, in the manufacturing method of the surface-modified molded article described in

[11] above, the polar group is preferably hydroxyl. By targeting a molded article formed of polyolefin with hydroxyl groups present on its surface, surface modification can be performed more efficiently.

[0032]

[13] Furthermore, in the method for manufacturing the surface-modified molded article according to any one of

[10] to

[12] above, the catalyst is preferably tris(pentafluorophenyl)borane. By using tris(pentafluorophenyl)borane as a catalyst, surface modification can be performed efficiently without corroding the surface of the molded article containing polyolefin.

[0033]

[14] Furthermore, in the manufacturing method of the surface-modified molded article in any of the above

[10] to

[13] , the surface-modified molded article is a molded article for medical use, and the surface-modified molded article may be a petri dish, tube, well plate, syringe or pipette tip.

[0034]

[15] Furthermore, in the manufacturing method of the surface-modified molded article in any of

[10] to

[14] above, it is preferable that at least one substituent of the hydrocarbon solvent is methyl. By using a hydrocarbon solvent having at least one methyl substituent, surface modification can be performed efficiently without corroding the surface of the molded article containing polyolefin.

[0035] Invention Effects

[0036] Therefore, according to the present invention, a surface treatment agent can be provided that can perform surface modification without excessively eroding the surface of molded articles containing polyolefins.

[0037] Furthermore, according to the present invention, a surface treatment agent kit can be provided that enables surface modification without excessively eroding the surface of molded articles containing polyolefins.

[0038] Furthermore, according to the present invention, it is possible to provide a surface-modified molded article comprising a polyolefin.

[0039] Furthermore, according to the present invention, a method for manufacturing a surface-modified molded article is provided, which enables surface modification without excessively eroding the surface of the molded article containing polyolefin. Detailed Implementation

[0040] The embodiments of the present invention will now be described in detail.

[0041] The surface treatment agent and surface treatment agent kit of the present invention can be used, for example, in the manufacturing method of the surface-modified molded article of the present invention. Furthermore, the surface-modified molded article of the present invention can be efficiently manufactured using the manufacturing method of the surface-modified molded article of the present invention.

[0042] (Surface treatment agent)

[0043] The surface treatment agent of the present invention is a surface treatment agent containing a hydrosilane compound and a borane catalyst, and may contain other components as desired. The hydrosilane compound has a Si-H group on which hydrogen atoms are bonded to silicon atoms in molecular structure A. This surface treatment agent is used for surface modification of molded articles containing polyolefins with polar groups on their surface. Furthermore, during surface modification, the surface treatment agent of the present invention is brought into contact with the molded article containing polyolefins with polar groups on its surface in a solvent containing at least 10% by volume of a hydrocarbon solvent having at least 5 carbon atoms with at least one substituent, causing a dehydrogenation condensation reaction between the molded article and the hydrosilane compound, thereby modifying the molded article through molecular structure A. Thus, by bringing the surface treatment agent containing the specified hydrosilane compound and borane catalyst into contact with the molded article containing polyolefins with polar groups on its surface in a solvent containing at least 10% by volume of a hydrocarbon solvent having at least 5 carbon atoms with at least one substituent, surface modification can be performed without excessively corroding the surface of the molded article containing polyolefins.

[0044] <Hydrosilane compounds>

[0045] The surface treatment agent of the present invention contains a hydrosilane compound having a Si-H group with hydrogen atoms bonded to the silicon atoms of molecular structure A, that is, a compound having a hydrosilyl group within the molecule. The hydrosilane compound can be represented by the following formula (I). The structural portion indicated by the dashed box in formula (I) is molecular structure A. In other words, molecular structure A corresponds to the portion of the hydrosilane compound that is removed from the surface through a dehydrogenation condensation reaction with a polar group present on the surface of the surface-modified object, i.e., the molded article. Furthermore, in molecular structure A, R, as a substituent... 1 R 2 Y 1 Y 2 Y 3 Y 4 Each of the following independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 30 carbon atoms, and -OR 4 R 4 This refers to a straight-chain or branched alkyl group having 1 to 30 carbon atoms. In this case, R... 1 R 2 R 4 Y1 Y 2 Y 3 Y 4 Alkyl groups with 1 to 30 carbon atoms, whether straight-chain or branched, can have fluorine atoms as substituents, and multiple carbon atoms can be replaced by oxygen atoms. However, there are no cases where oxygen atoms are substituted in more than two consecutive forms. 1 X 2 X 3 Each can be used independently to represent -O- or a single bond, where l represents an integer greater than 1 and less than 300, and n and m represent integers greater than 0 and less than 300. Where R... 1 R 2 Y 1 Y 2 Y 3 Y 4 At least one of them is not a hydrogen atom.

[0046] [Chemical Formula 2]

[0047]

[0048] In equation (I) above, R 1 R 2 Y 1 Y 2 Y 3 Y 4 Each is independently a straight-chain or branched alkyl group having 20 or fewer carbon atoms, or -OR 4 (R 4 R is a straight-chain or branched alkyl group with 20 or fewer carbon atoms. 1 R 2 R 4 Y 1 Y 2 Y 3 Y 4 Alkyl groups with 20 or fewer carbon atoms, whether straight-chain or branched, can have fluorine atoms as substituents. Furthermore, multiple carbon atoms can be replaced with oxygen atoms. However, it is preferable that no oxygen atoms are substituted in two or more consecutive forms.

[0049] Furthermore, in the above equation (I), R 1 R 2 Y 1 Y 2 Y 3 Y 4 Each is independently a straight-chain or branched alkyl group having 20 or fewer carbon atoms, or -OR 4 (R 4 R is a straight-chain or branched alkyl group with 20 or fewer carbon atoms.1 R 2 R 4 Y 1 Y 2 Y 3 Y 4 Alkyl groups with 20 or fewer carbon atoms, whether straight-chain or branched, can have fluorine atoms as substituents. Furthermore, 8 or fewer carbon atoms can be replaced with oxygen atoms. However, it is more preferable that no oxygen atoms are substituted in two or more consecutive forms.

[0050] Furthermore, in the above equation (I), R 1 R 2 Y 1 Y 2 Y 3 Y 4 Each is independently a straight-chain or branched alkyl group having 14 or fewer carbon atoms, or -OR 4 (R 4 R is a straight-chain or branched alkyl group with 14 or fewer carbon atoms. 1 R 2 R 4 Y 1 Y 2 Y 3 Y 4 Alkyl groups with 14 or fewer carbon atoms, whether straight-chain or branched, can have fluorine atoms as substituents. Furthermore, multiple carbon atoms can be replaced with oxygen atoms. However, it is even more preferable that no oxygen atoms are substituted in two or more consecutive forms.

[0051] Furthermore, in the above equation (I), R 1 R 2 Y 1 Y 2 Y 3 Y 4 Each is independently a straight-chain or branched alkyl group having 14 or fewer carbon atoms, or -OR 4 (R 4 R is a straight-chain or branched alkyl group with 14 or fewer carbon atoms. 1 R 2 R 4 Y 1 Y 2 Y 3 Y 4 Alkyl groups with 14 or fewer carbon atoms, whether straight-chain or branched, can have fluorine atoms as substituents. Furthermore, five or fewer carbon atoms can be replaced with oxygen atoms. However, it is particularly preferable that no oxygen atoms are substituted in two or more consecutive forms.

[0052] Furthermore, in the above equation (I), R is the optimal choice. 1 R 2 Y 1 Y 2 Y 3 Y 4 Each can be independently classified as having a methoxy, ethoxy, propoxy, or -(OCH2CH2) group. x -OCH3, -(OCH2CH2) x -H as a substituent for methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, or -OR 4 (R 4 It contains methoxy, ethoxy, propoxy, and -(OCH2CH2) groups. x -OCH3, -(OCH2CH2) x -H can be a substituent for methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, or -(CH2CH2O). x CH3、-(CH2CH2O) x -CH3, -(CH2CH2O) x -CH2CH3), x represents an integer from 1 to 6, and any number of hydrogen atoms can be replaced by fluorine atoms.

[0053] In formula (I) above, l + m is preferably 1 or more and 200 or less, more preferably 1 or more and 150 or less. n is also preferably 1 or more and 200 or less, more preferably 1 or more and 150 or less.

[0054] As for the hydrosilane compounds that can be represented by the above formula (I), there are no particular limitations. Examples include polymethylhydrosiloxane represented by the following formula (A) and octadecylhydrosilane represented by the following formula (B).

[0055] [Chemical Formula 3]

[0056]

[0057] Furthermore, for example, when using polymethylhydrosiloxane represented by the above formula (A) as a prescribed hydrosilane compound to modify the surface of a molded article containing polyolefins with polar groups (e.g., hydroxyl groups) on the surface, the molecular structure A (within the dashed box) shown in the figure below modifies the surface of the molded article.

[0058] [Chemical Formula 4]

[0059]

[0060] Furthermore, for example, when using octadecylhydrosilane represented by the above formula (B) as the prescribed hydrosilane compound to modify the surface of a polyolefin-containing molded article having polar groups (e.g., hydroxyl groups) on its surface, the molecular structure A (within the dashed box) shown in the figure below modifies the surface of the molded article.

[0061] [Chemical Formula 5]

[0062]

[0063] Furthermore, the amount of hydrosilane compound in the treatment solution is not particularly limited within the range where surface treatment is possible, for example, it can be 0.005 mol / L or more and 0.30 mol / L or less, preferably 0.005 mol / L or more and 0.20 mol / L or less.

[0064] <Boronane Catalyst>

[0065] The borane catalyst contained in the surface treatment agent of the present invention is not particularly limited, and examples include at least one selected from trichloroborane, tribromoborane, trifluoroborane, and tris(pentafluorophenyl)borane ((C6F5)3B). Among these, tris(pentafluorophenyl)borane ((C6F5)3B) is preferred because it can perform surface modification of the molded article at a relatively low temperature and for a short time, resulting in excellent modification efficiency. The amount of borane catalyst varies depending on the number of hydroxyl groups on the surface to be treated, the structure of molecular structure A, the reactivity of the silane, and the amount of molecular structure A to be introduced, etc., and is not particularly limited as long as the concentration in the specified solvent for performing the surface treatment is within the normal range. For example, it is 0.0005 mol / L or more and 0.02 mol / L or less, preferably 0.001 mol / L or more and 0.005 mol / L or less.

[0066] Solvent

[0067] The solvent used when the surface treatment agent of the present invention comes into contact with the specified molded article to be surface treated needs to contain 10% by volume or more of a hydrocarbon solvent having at least one substituent and a total carbon number of 5 or more.

[0068] As a substituent of a hydrocarbon solvent having at least one substituent with a total carbon number of 5 or more, a straight-chain or branched alkyl group with 5 or fewer carbon atoms is preferred, a straight-chain or branched alkyl group with 3 or fewer carbon atoms is more preferred, ethyl or methyl is even more preferred, and methyl is most preferred. If the number of carbon atoms of the substituent of the hydrocarbon solvent is below the above-mentioned upper limit, the surface erosion of the molded article specified in the surface modification treatment can be effectively suppressed, and the surface condition of the obtained surface-modified molded article can be improved.

[0069] The hydrocarbon solvent having at least one substituent and a total carbon number of 5 or more preferably has 30 or fewer substituents, more preferably 25 or fewer, even more preferably 10 or fewer, and most preferably 8 or fewer. If the number of substituents in the hydrocarbon solvent is within the above range, the surface erosion of the molded article specified in the surface modification treatment can be effectively suppressed, and the surface condition of the obtained surface-modified molded article can be improved.

[0070] Furthermore, the total carbon number of the hydrocarbon solvent having at least one substituent and a total carbon number of 5 or more is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less. If the total carbon number of the hydrocarbon solvent is below the above-mentioned upper limit, the surface erosion of the molded article specified in the surface modification treatment can be effectively suppressed, and the surface condition of the obtained surface-modified molded article can be improved.

[0071] As a hydrocarbon solvent having at least one substituent and a total carbon number of 5 or more that satisfies the above conditions, there are no particular limitations, but examples include 2-methylbutane (1 substituent, 5 total carbon atoms), 2-methylpentane (1 substituent, 6 total carbon atoms), 2,2-dimethylbutane (2 substituents, 6 total carbon atoms), 2,2-dimethylpentane (2 substituents, 7 total carbon atoms), 2,2-dimethylhexane (2 substituents, 8 total carbon atoms), 2,2,3-trimethylbutane (3 substituents, 7 total carbon atoms), and 2,3... 4-Trimethylpentane (3 substituents, 8 total carbon atoms), 2,2,4-trimethylpentane (3 substituents, 8 total carbon atoms), 2,2,4-trimethylhexane (3 substituents, 9 total carbon atoms), 2,2,4,4-tetramethylpentane (4 substituents, 9 total carbon atoms), 2,6,10,14-tetramethylpentadecane (4 substituents, 19 total carbon atoms), squalane (6 substituents, 30 total carbon atoms), and 2,2,4,4,6,8,8-heptamethylnonane (7 substituents, 16 total carbon atoms). In addition, isohexanes, isooctanes, liquid paraffins, etc., can also be used as solvents sold as mixtures containing substituented hydrocarbons. These can be used individually or in combination.

[0072] Furthermore, when the surface treatment agent of the present invention comes into contact with the specified molded article to be surface treated, the proportion of the specified hydrocarbon solvent in the solvent is preferably 15% by volume or more, more preferably 20% by volume or more, further preferably 35% by volume or more, and particularly preferably 45% by volume or more. If the specified proportion of hydrocarbon solvent is at or above the aforementioned lower limit, the erosion of the surface of the specified molded article during the surface modification treatment can be effectively suppressed, and the surface condition of the resulting surface-modified molded article can be improved.

[0073] Furthermore, when the surface treatment agent of the present invention comes into contact with the specified molded article to be surface treated, the solvent used is not particularly limited to the hydrocarbon solvents specified above, and examples of unsubstituent hydrocarbon solvents can be given. Examples of such hydrocarbon solvents include, for instance, n-heptane, n-decane, and n-undecane, which are unsubstituent hydrocarbon solvents with 20 or fewer carbon atoms, as well as solvents such as toluene, which have excellent solubility for borane catalysts. These can be used alone or in combination. In addition, when aromatic hydrocarbons such as toluene, which are used to dissolve the borane catalyst, are present in the dehydrogenation condensation reaction solvent, their amount is preferably small, for example, preferably 3.0% by volume or less of the dehydrogenation condensation reaction solvent.

[0074] Molded Products

[0075] Furthermore, the molded article targeted by the surface treatment agent of the present invention is a polyolefin-containing molded article with polar groups present on its surface. In addition to polyolefin, the molded article may contain any other resin. There are no particular limitations on the polar groups; hydroxyl and carbonyl groups are examples. From the viewpoint of surface modification efficiency, hydroxyl groups are particularly preferred. In addition, in this specification, regarding a polyolefin-containing molded article, "having polar groups on its surface" means that polar groups are present in at least a portion of the surface of the molded article. The hydroxyl groups on the surface of the molded article are those that can be introduced into the surface of the molded article during the molding process. Furthermore, when the constituent material of the molded article, i.e., polyolefin or other resin, has polar groups as substituents, at least a portion of the surface of the molded article may also have polar groups. Additionally, the polar groups present in at least a portion of the surface of the molded article may originate from residues of additives such as polymerization initiators used when synthesizing the constituent material of the molded article, i.e., polyolefin or other resin. Alternatively, polar groups can be introduced onto the surface of the molded article by performing surface treatments such as plasma treatment, corona treatment, and light irradiation on the molded article formed from polyolefins and any other resins that do not have polar groups.

[0076] The proportion of polyolefin in the molded body is not particularly limited, but it is preferably the main component of the molded body, i.e., more than 50% by mass, more preferably more than 70% by mass, or 100% by mass.

[0077] Furthermore, the polyolefin constituting the molded article is not particularly limited, and cyclic olefin (co)polymers can be cited as examples. According to the surface treatment agent of the present invention, for molded articles with cyclic olefin (co)polymers as the main component, surface modification can be performed well without causing surface roughness. Examples of cyclic olefin (co)polymers include (1) norbornene polymers, (2) monocyclic cyclic olefin polymers, (3) cyclic conjugated diene polymers, (4) vinyl alicyclic hydrocarbon polymers, and hydrides of (1) to (4). Among these, norbornene polymers and their hydrides are preferred because they can impart high heat resistance and mechanical strength to the resulting molded articles.

[0078] (1) Norbornene polymers

[0079] Norbornene polymers are polymers formed by polymerizing monomers with a norbornene skeleton, namely norbornene monomers. They are broadly classified into norbornene polymers obtained by ring-opening polymerization and norbornene polymers obtained by addition polymerization.

[0080] Examples of norbornene polymers obtained by ring-opening polymerization include ring-opening polymers of norbornene monomers, ring-opening polymers of norbornene monomers and other monomers capable of ring-opening copolymerization therewith, and their hydrides. Examples of norbornene polymers obtained by addition polymerization include addition polymers of norbornene monomers, and addition polymers of norbornene monomers and other monomers capable of copolymerization therewith. Among these, ring-opening polymer hydrides of norbornene monomers are preferred from the viewpoints of heat resistance and mechanical strength.

[0081] Examples of norbornene monomers that can be used to synthesize norbornene polymers include: bicyclo[2.2.1]hept-2-ene (commonly known as norbornene), 5-methyl-bicyclo[2.2.1]hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]hept-2-ene, 5-ethyl-bicyclo[2.2.1]hept-2-ene, 5-ethylene-bicyclo[2.2.1]hept-2-ene, 5-vinyl-bicyclo[2.2.1]hept-2-ene, 5-propenylbicyclo[2.2.1]hept-2-ene, 5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene, 5-cyanobicyclo[2.2.1]hept-2-ene, and 5-methyl-5-methoxycarbonyl-bicyclo[2.2.1]hept-2-ene, among other bicyclic monomers.

[0082] Three Rings [4.3.0] 1,6 .1 2,5 Tricyclic monomers such as dec-3,7-diene (commonly known as dicyclopentadiene), 2-methyldicyclopentadiene, 2,3-dimethyldicyclopentadiene, and 2,3-dihydroxydicyclopentadiene;

[0083] Fourth Ring Road [4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene (tetracyclododecene), tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Methyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Ethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Ethylenetetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8,9-Dimethyltetracyclo[4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene, 8-Ethyl-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Ethylene-9-methyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 8-Methyl-8-carboxymethyltetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-Dodecene, 7,8-benzotricyclo[4.3.0.1 2,5 Dec-3-ene (commonly known as methylbridged tetrahydrofluorene: also called 1,4-methylbridged-1,4,4a,9a-tetrahydrofluorene), 1,4-methylbridged-8-methyl-1,4,4a,9a-tetrahydrofluorene, 1,4-methylbridged-8-chloro-1,4,4a,9a-tetrahydrofluorene, 1,4-methylbridged-8-bromo-1,4,4a,9a-tetrahydrofluorene, etc., are tetracyclic monomers.

[0084] Other monomers that can undergo ring-opening copolymerization with norbornene monomers include monocyclic cycloolefin monomers such as cyclohexene, cycloheptene, cyclooctene, 1,4-cyclohexadiene, 1,5-cyclooctadiene, 1,5-cyclodecadiene, 1,5,9-cyclododecanetriene, and 1,5,9,13-cyclohexadecanetetraene.

[0085] These monomers can have one or more substituents. Examples of substituents include alkyl, alkylene group, aryl, silyl, alkoxycarbonyl, and alkoxylidene group.

[0086] Other monomers capable of addition copolymerization with norbornene monomers include: α-olefin monomers with 2 to 20 carbon atoms, such as ethylene, propylene, 1-butene, 1-pentene, and 1-hexene; cyclobutene, cyclopentene, cyclohexene, cyclooctene, and tetracyclo[9.2.1.0] 2,10 .0 3,8 Cycloolefin monomers such as tetradecyl-3,5,7,12-tetraene (also known as 3a,5,6,7a-tetrahydro-4,7-methylbridge-1H-indene); non-conjugated diene monomers such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene.

[0087] Among these, α-olefin monomers are preferred, and ethylene is more preferred, as other monomers capable of addition copolymerization with norbornene monomers.

[0088] These monomers may have one or more substituents. Examples of substituents include alkyl, alkylene, aryl, silyl, alkoxycarbonyl, and alkylidene groups.

[0089] Ring-opening polymers of norbornene monomers, or ring-opening polymers of norbornene monomers and other monomers capable of ring-opening copolymerization, can be obtained by polymerizing monomer components in the presence of a known ring-opening polymerization catalyst. As ring-opening polymerization catalysts, catalysts such as those composed of halides of metals like ruthenium and osmium with nitrates or acetylacetone compounds and a reducing agent, or catalysts composed of halides of metals like titanium, zirconium, tungsten, and molybdenum with organoaluminum compounds, can be used.

[0090] Ring-opening polymer hydrides of norbornene monomers can usually be obtained by hydrogenating carbon-carbon unsaturated bonds by adding a known hydrogenation catalyst containing transition metals such as nickel and palladium to the polymerization solution of the above-mentioned ring-opening polymer.

[0091] Addition polymers of norbornene monomers, or addition polymers of norbornene monomers with other monomers that can copolymerize therewith, can be obtained by polymerizing the monomer components in the presence of a known addition polymerization catalyst. Catalysts such as those composed of titanium, zirconium, or vanadium compounds and organoaluminum compounds can be used as addition polymerization catalysts.

[0092] (2) Monocyclic cyclic olefin polymers

[0093] As a monocyclic cyclic olefin polymer, it can be an addition polymer of monocyclic cyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

[0094] (3) Cyclic conjugated diene polymers

[0095] As cyclic conjugated diene polymers, polymers and their hydrides obtained by 1,2- or 1,4-addition polymerization of cyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene can be used.

[0096] (4) Vinyl alicyclic hydrocarbon polymers

[0097] Examples of vinyl alicyclic hydrocarbon polymers include polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane, and their hydrides; and hydrides of the aromatic ring portion of polymers of vinyl aromatic monomers such as styrene and α-methylstyrene. Vinyl alicyclic hydrocarbon polymers can also be copolymers of these monomers with other monomers that can be copolymerized.

[0098] There are no particular limitations on the molecular weight of the cycloolefin (co)polymer. The weight-average molecular weight, calculated as that of polyisoprene by gel permeation chromatography of a cyclohexane solution (or toluene solution if the polymer is insoluble), is typically 5000 or more, preferably 5000 or more and 500,000 or less, more preferably 8000 or more and 200,000 or less, and particularly preferably 10,000 or more and 100,000 or less. When the weight-average molecular weight is within this range, a high balance between mechanical strength and processability is achieved, which is suitable.

[0099] The glass transition temperature of the cycloolefin (co)polymer can be appropriately selected according to its intended use, typically above 50°C and below 300°C, preferably above 80°C and below 280°C, particularly preferably above 90°C and below 250°C, and even more preferably above 90°C and below 200°C. When the glass transition temperature is within this range, a high balance between heat resistance and processability is achieved, which is suitable.

[0100] In addition, the glass transition temperature of cyclic olefin (co)polymers can be determined based on JIS K 7121.

[0101] The aforementioned polyolefins can be used individually or in combination of two or more. Furthermore, depending on the intended use of the molded product, polyolefins can be formulated with conventionally used additives such as soft polymers, antioxidants, ultraviolet absorbers, light stabilizers, near-infrared absorbers, release agents, colorants such as dyes or pigments, plasticizers, antistatic agents, and fluorescent whitening agents.

[0102] The shape of the molded article is not particularly limited. In this specification, the term "molded article" refers not only to the so-called product, but also to the state of the substrate that serves as the material for the product. Therefore, for example, the molded article may have the shape of a plate, block, porous body, sheet, granules, powder, and fiber as the substrate that serves as the material for the product. Alternatively, the molded article may also have the shape of a petri dish, tube, well plate, syringe, and pipette tip as the product.

[0103] (Manufacturing method of surface-modified molded articles, surface treatment agent kit, and surface-modified molded articles)

[0104] Hereinafter, as an example, the manufacturing method of the surface-modified molded article, the surface treatment agent kit, and the surface-modified molded article of the present invention will be described in sequence in the form of the surface treatment agent of the present invention being packaged as a surface treatment agent kit.

[0105] The method for manufacturing a surface-modified molded article of the present invention is characterized by comprising the following step (surface modification step): in a solvent containing 10% by volume or more of a hydrocarbon solvent having at least one substituent and a total carbon number of 5 or more, in the presence of a borane catalyst, a molded article formed of a polyolefin having polar groups on its surface is brought into contact with a hydrosilane compound having Si-H groups having hydrogen atoms bonded to silicon atoms in molecular structure A, thereby causing a dehydrogenation condensation reaction between the molded article and the hydrosilane compound, thereby forming the aforementioned molded article whose surface is modified by molecular structure A. According to this method for manufacturing a surface-modified molded article, surface modification can be performed without excessively eroding the surface of the molded article containing polyolefin.

[0106] <Surface Finishing Process>

[0107] In the surface modification process, the surface of the molded article is modified using the surface treatment agent kit of the present invention, which contains agent A, comprising a hydrosilane compound, and agent B, comprising a borane catalyst. The hydrosilane compound has Si-H groups on silicon atoms bonded to them in molecular structure A. According to this surface treatment agent kit of the present invention, surface modification can be performed without excessively eroding the surface of the molded article containing polyolefins.

[0108] [Surface Treatment Agent Kit]

[0109] The surface treatment agent kit of the present invention comprises agent A and agent B, each containing at least one organic solvent. The organic solvent contained in agent A can be the same as or different from the organic solvent contained in agent B, but at least 10% by volume of the total organic solvent contained in agents A and B must be a "hydrocarbon solvent having at least one substituent and a total carbon number of 5 or more". The surface treatment agent kit modifies the surface of the molded article through molecular structure A by contacting the aforementioned agent A and agent B with a "molded article containing a polyolefin having polar groups on its surface" as described above, causing a dehydrogenation condensation reaction between the molded article and the hydrosilane compound. According to this surface treatment agent kit, surface modification can be performed without excessively corroding the surface of the molded article containing the polyolefin.

[0110] Agent A

[0111] The surface treatment agent kit of the present invention contains a hydrosilane compound having a Si-H group on which hydrogen atoms are bonded to silicon atoms in molecular structure A. Examples of such hydrosilane compounds include those described above. Furthermore, examples of hydrocarbon solvents having a total carbon number of 5 or more and having at least one substituent can be used as organic solvents incorporated in agent A. The concentration of the hydrosilane compound in agent A is not particularly limited and can be 0.005 mol / L or more and 0.300 mol / L or less.

[0112] - Agent B

[0113] Agent B, constituting the surface treatment agent kit of the present invention, contains a borane catalyst. Examples of borane catalysts include those described above. Furthermore, the organic solvent incorporated in Agent B is not particularly limited as long as it can dissolve the borane catalyst. Examples of such solvents include toluene, ethyl acetate, and cyclopentyl methyl ether. The concentration of the borane catalyst in Agent B is not particularly limited and can be 0.005 mol / L or more and 0.500 mol / L or less.

[0114] - Organic solvent composition

[0115] Furthermore, with the total organic solvent content in the aforementioned Agent A and Agent B being 100% by volume, at least 10% by volume of a hydrocarbon solvent having at least 5 carbon atoms and having at least one substituent is required. From the viewpoint of making the surface condition of the obtained surface-modified molded article better, at least 15% by volume is preferred, more preferably 20% by volume is preferred, further preferably 35% by volume is preferred, and particularly preferably 45% by volume is preferred.

[0116] In the surface finishing process, agent B is added to agent A to obtain a surface treatment agent. Then, when the obtained surface treatment agent is applied to a molded article to be surface treated, the molded article can be pre-dried arbitrarily. Surface treatment can be performed at temperatures below 70°C. Furthermore, the surface treatment temperature can be below 40°C, below 30°C, or even room temperature (25°C). In addition, the surface treatment time can be, for example, 5 hours or less, 3 hours or less, or even 1 hour or less.

[0117] After the surface treatment time, the surface treatment agent is removed, and then the surface is rinsed with an organic solvent to complete the surface treatment. For the initial rinse, a hydrocarbon solvent with a total carbon number of 5 or more and having at least one methyl group as a substituent is preferably used. The solvent used for the second and subsequent rinses is not particularly limited and can be appropriately selected according to the application.

[0118] Then, the surface-modified molded article is dried by drying methods such as air drying. The surface-modified molded article of the present invention, obtained through this process, is formed by introducing the following molecular structure A onto the surface via -O- bonds. In molecular structure A, R acts as a substituent. 1 R 2 Y 1 Y 2 Y 3 Y 4 Each of the following independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 30 carbon atoms, and -OR 4 R 4 This refers to a straight-chain or branched alkyl group having 1 to 30 carbon atoms. In this case, R... 1 R 2 R 4 Y 1 Y 2 Y 3 Y 4 Alkyl groups with 1 to 30 carbon atoms, whether straight-chain or branched, can have fluorine atoms as substituents, and multiple carbon atoms can be replaced by oxygen atoms. However, there are no cases where oxygen atoms are substituted in more than two consecutive forms. 1 X 2 X 3 Each can be used independently to represent -O- or a single bond, where l represents an integer greater than 1 and less than 300, and n and m represent integers greater than 0 and less than 300. Where R... 1 R 2 Y 1 Y 2 Y 3 Y 4 At least one of them is not a hydrogen atom. Furthermore, in the diagram below, "*" indicates a bonding location with the surface of the molded article.

[0119] [Chemical Formula 6]

[0120]

[0121] Furthermore, the resulting surface-modified molded articles have low surface roughness, meaning the surface is not excessively eroded by organic solvents. Therefore, they are suitable for medical applications. In other words, the surface-modified molded articles of the present invention are preferably medical petri dishes, tubes, well plates, syringes, or pipette tips.

[0122] Example

[0123] The present invention will now be described in detail based on embodiments, but the present invention is not limited to these embodiments. Furthermore, in the following description, unless otherwise specified, "%" and "parts" refer to quantities based on mass.

[0124] Furthermore, in the embodiments and comparative examples, various properties were measured and evaluated by the following methods.

[0125] (Contact angle measurement used to determine the success of surface treatment)

[0126] In the examples and comparative examples, to determine whether the surface treatment was properly completed, the water droplet contact angle was measured before and after the surface treatment, and the change was calculated. The hydrosilane compounds used in the examples and comparative examples, when introduced onto the surface of the molded article, enhance the surface's hydrophobicity. Therefore, to determine whether the surface treatment was properly completed, it is necessary to confirm whether the water droplet contact angle after surface treatment is larger than the water droplet contact angle before surface treatment. The specific procedures are as follows.

[0127] The bottom of the petri dish was cut into 1.5 cm square pieces to obtain test pieces. Test pieces were prepared in two ways: untreated test pieces and test pieces treated according to the conditions of each embodiment and comparative example. For the surface-treated test pieces, the inner side of the petri dish (the side in contact with the treatment solution) was used as the surface of the test piece before cutting. The contact angle of pure water on the surface of the test piece was measured using an automatic contact angle meter (DM-501Hi; manufactured by Kyowa Interface Science Co., Ltd.). The measurement was performed using the droplet method, where 2.0 μL of water was dropped and the contact angle was measured after 3 seconds. Five identical measurements were performed on each test piece, and the arithmetic mean was used as the representative value of the contact angle. Based on the measurement results, the value (°) of the contact angle after surface treatment minus the contact angle before surface treatment was obtained and summarized in Tables 1-8.

[0128] (Haze measurement used to confirm surface condition)

[0129] The haze value is used to determine whether the surface of the molded product has been corroded due to surface treatment. The haze value of the petri dish was measured using a haze meter (SH7000; manufactured by Nippon Denshoku Kogyo Co., Ltd.) on the bottom surface of the petri dish (1.8 mm thick). Specifically, the diffuse light transmittance (Td; %) and the total light transmittance (Tt; %) were measured separately, and the calculated value of Td / Tt × 100 (%) was used as the haze value. Here, total light transmittance refers to the transmittance of all transmitted light, and diffuse light transmittance refers to the value after excluding parallel light transmittance from the total light transmittance. Parallel light transmittance refers to the transmittance of light that passes straight through the material.

[0130] In addition, the same measurement was performed three times on each petri dish, and the arithmetic mean was used as the representative value of haze. The measurement results are summarized in Tables 1-8.

[0131] If the haze value is below 1.5, the surface is considered not to be excessively corroded and is deemed "qualified"; if the haze value is above 1.5, the surface is considered to be corroded and is deemed "unqualified".

[0132] (Preparation of molded products)

[0133] As the surface-treated product, a circular petri dish with a 35mm ϕ cap, formed from a cyclic olefin polymer or a cyclic olefin copolymer, was used. The petri dish made of cyclic olefin polymer was manufactured by injection molding ZEONEX 690R (manufactured by Zeon Corporation, Japan). The petri dish made of cyclic olefin copolymer was manufactured by injection molding TOPAS 6013M-07 (manufactured by Polyplastics Corporation, Japan). The molded products used in the tests were those that had been vacuum-dried at 105°C for 6 hours beforehand. Furthermore, the test pieces used for the contact angle measurement were prepared separately from the test pieces used in the respective examples and comparative examples. In addition, the polar groups on the surface of the surface-treated product could be confirmed by X-ray photoelectron spectroscopy.

[0134] (Preparation of the catalyst solution as agent B)

[0135] In a glove box purged with nitrogen, 6.5 g (12.70 mmol) of tris(pentafluorophenyl)borane (manufactured by Tokyo Chemical Industry Co., Ltd.) as a borane catalyst was added to a 50 ml volumetric flask, followed by ultra-dehydrated toluene (manufactured by Fujifilm and Kohden Chemical Co., Ltd.) as an organic solvent, and dissolved to a total volume of 50 ml. The solution was then transferred to a glass bottle with a rubber stopper and sealed.

[0136] (Example 1)

[0137] <Preparation of the surface treatment solution as agent A>

[0138] At room temperature, 0.20 g (0.079 mmol) of polymethylhydrosiloxane (PMHS; manufactured by Momentive Performance Materials) was added to a 15 ml Teflon (registered trademark) container. Then, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was added and dissolved. 0.062 ml of the catalyst solution (as agent B) prepared in the "Preparation of Catalyst Solution" section above was drawn up using a syringe, added to this solution, and mixed to prepare the surface treatment agent.

[0139] <Surface Treatment Process>

[0140] In a round petri dish with a 35mm ϕ cap, prepared by vacuum drying using a ZEONEX 690R (manufactured by Zeon Corporation of Japan) according to the preparation procedures described above, 5 ml of the surface treatment solution prepared in the "Preparation of Surface Treatment Solution" section was added at room temperature. The petri dish was then capped and allowed to stand. After reacting for 1 hour, the treatment solution was drained from the petri dish. The dish was then washed once with 2-methylbutane and twice with diisopropyl ether. The diisopropyl ether adhering to the petri dish was blown away with nitrogen gas to dry it, thus preparing a sample for contact angle and haze measurement.

[0141] (Example 2)

[0142] In the "Preparation of Surface Treatment Solution" of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of 2-methylpentane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the one-time cleaning with 2-methylbutane in the "Surface Treatment Step" was replaced with 2-methylpentane. Otherwise, the same procedures were performed to prepare the sample. Furthermore, various evaluations were conducted in the same manner as in the Examples.

[0143] (Example 3)

[0144] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of 2,2-dimethylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with cleaning with 2,2-dimethylbutane. Otherwise, the same operation was performed to prepare the sample.

[0145] (Example 4)

[0146] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of 2,2-dimethylpentane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with cleaning with 2,2-dimethylpentane. Otherwise, the same operation was performed to prepare the sample.

[0147] (Example 5)

[0148] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of 2,2-dimethylhexane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with cleaning with 2,2-dimethylhexane. Otherwise, the same operation was performed to prepare the sample.

[0149] (Example 6)

[0150] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of 2,2,3-trimethylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with cleaning with 2,2,3-trimethylbutane. Otherwise, the same operation was performed to prepare the sample.

[0151] (Example 7)

[0152] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of 2,3,4-trimethylpentane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with cleaning with 2,3,4-trimethylpentane. Otherwise, the same operation was performed to prepare the sample.

[0153] (Example 8)

[0154] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of 2,2,4-trimethylpentane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with cleaning with 2,2,4-trimethylpentane. Otherwise, the same operation was performed to prepare the sample.

[0155] (Example 9)

[0156] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of 2,2,4-trimethylhexane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with cleaning with 2,2,4-trimethylhexane. Otherwise, the same operation was performed to prepare the sample.

[0157] (Example 10)

[0158] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of 2,2,4,4-tetramethylpentane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with cleaning with 2,2,4,4-tetramethylpentane. Otherwise, the same operation was performed to prepare the sample.

[0159] (Example 11)

[0160] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of 2,6,10,14-tetramethylpentadecane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with cleaning with 2,6,10,14-tetramethylpentadecane. Otherwise, the same operation was performed to prepare the sample.

[0161] (Example 12)

[0162] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of squalane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with squalane. Otherwise, the same operation was performed to prepare the sample.

[0163] (Example 13)

[0164] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of 2,2,4,4,6,8,8-heptamethylnonane (manufactured by Tokyo Chemical Industry Co., Ltd.), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with cleaning with 2,2,4,4,6,8,8-heptamethylnonane. Otherwise, the same operation was performed to prepare the sample.

[0165] (Example 14)

[0166] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of n-heptane / 2,2-dimethylpentane = 50 / 50 (volume ratio), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with n-heptane / 2,2-dimethylpentane = 50 / 50 (volume ratio). Otherwise, the same operation was performed to prepare the sample.

[0167] (Example 15)

[0168] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of n-heptane / 2,2-dimethylpentane = 70 / 30 (volume ratio), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with n-heptane / 2,2-dimethylpentane = 70 / 30 (volume ratio). Otherwise, the same operation was performed to prepare the sample.

[0169] (Example 16)

[0170] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of n-heptane / 2,2-dimethylpentane = 90 / 10 (volume ratio), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with n-heptane / 2,2-dimethylpentane = 90 / 10 (volume ratio). Otherwise, the same operation was performed to prepare the sample.

[0171] (Example 17)

[0172] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of n-heptane / 2,2,4-trimethylpentane = 50 / 50 (volume ratio), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with n-heptane / 2,2,4-trimethylpentane = 50 / 50 (volume ratio). Otherwise, the same operation was performed to prepare the sample.

[0173] (Example 18)

[0174] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of n-heptane / 2,2,4-trimethylpentane = 70 / 30 (volume ratio), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with n-heptane / 2,2,4-trimethylpentane = 70 / 30 (volume ratio). Otherwise, the same operation was performed to prepare the sample.

[0175] (Example 19)

[0176] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of n-heptane / 2,2,4-trimethylpentane = 90 / 10 (volume ratio), and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with n-heptane / 2,2,4-trimethylpentane = 90 / 10 (volume ratio). Otherwise, the same operation was performed to prepare the sample.

[0177] (Comparative Example 1)

[0178] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of n-heptane, and the cleaning with 2-methylbutane in the “Surface Treatment Step” was replaced with n-heptane. Otherwise, the same operation was performed to prepare the sample.

[0179] (Comparative Example 2)

[0180] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of n-decane, and the washing with 2-methylbutane in the “Surface Treatment” step was replaced with n-decane. Otherwise, the same operation was performed to prepare the sample.

[0181] (Comparative Example 3)

[0182] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of n-undecane, and the washing with 2-methylbutane in the “Surface Treatment” step was replaced with n-undecane. Otherwise, the same operation was performed to prepare the sample.

[0183] (Comparative Example 4)

[0184] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of cyclohexane, and the washing with 2-methylbutane in the “Surface Treatment” step was replaced with cyclohexane. Otherwise, the same operation was performed to prepare the sample.

[0185] (Comparative Example 5)

[0186] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of toluene, and the washing with 2-methylbutane once in the “Surface Treatment” step was replaced with toluene. Otherwise, the same operation was performed to prepare the sample.

[0187] (Comparative Example 6)

[0188] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of dichloromethane, and the cleaning with 2-methylbutane in the “Surface Treatment” step was replaced with dichloromethane. Otherwise, the same operation was performed to prepare the sample.

[0189] (Comparative Example 7)

[0190] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of tetrahydrofuran, and the washing with 2-methylbutane once in the “Surface Treatment” step was replaced with tetrahydrofuran. Otherwise, the same operation was performed to prepare the sample.

[0191] (Comparative Example 8)

[0192] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of methyl ethyl ketone, and the washing with 2-methylbutane once in the “Surface Treatment” step was replaced with methyl ethyl ketone. Otherwise, the same operation was performed to prepare the sample.

[0193] (Comparative Example 9)

[0194] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of cyclopentanone, and the washing with 2-methylbutane in the “Surface Treatment” step was replaced with cyclopentanone. Otherwise, the same operation was performed to prepare the sample.

[0195] (Comparative Example 10)

[0196] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of acetonitrile, and the cleaning with 2-methylbutane in the “Surface Treatment” step was replaced with acetonitrile. Otherwise, the same operation was performed to prepare the sample.

[0197] (Comparative Example 11)

[0198] In the “Preparation of Surface Treatment Solution” of Example 1, 8.0 ml of 2-methylbutane (manufactured by Tokyo Chemical Industry Co., Ltd.) was replaced with 8.0 ml of N,N-dimethylacetamide, and the washing with 2-methylbutane in the “Surface Treatment” step was replaced with N,N-dimethylacetamide. Otherwise, the same operation was performed to prepare the sample.

[0199] (Examples 20-38 and Comparative Examples 12-22)

[0200] In Examples 1-19 and Comparative Examples 1-11 above, the circular petri dishes with 35mm ϕ lids formed by vacuum drying ZEONEX 690R (manufactured by Zeon Corporation, Japan) were replaced with petri dishes formed by TOPAS6013M-07 (manufactured by Polyplastics Corporation, Japan), which is a cyclic olefin copolymer. Otherwise, the same operations were performed as in Examples 1-19 and Comparative Examples 1-11 to prepare the samples.

[0201] (Examples 39-57 and Comparative Examples 23-33)

[0202] In the “Preparation of Surface Treatment Solution”, 0.20 g (0.079 mmol) of polymethylhydrosiloxane (PMHS; manufactured by Momentive Performance Materials) was replaced with 0.20 g (0.64 mmol) of dimethyloctadecylhydrosilane (manufactured by Aldrich). Otherwise, the same operation was performed as in Examples 1-19 and Comparative Examples 1-11 to prepare the samples.

[0203] (Examples 58-76 and Comparative Examples 34-44)

[0204] In the “Preparation of Surface Treatment Solution” of Example 1, 0.20 g (0.079 mmol) of polymethylhydrosiloxane (PMHS; manufactured by Momentive Performance Materials) was replaced with 0.20 g (0.64 mmol) of dimethyloctadecylhydrosilane (manufactured by Aldrich). Otherwise, the same operation was performed as in Examples 20-38 and Comparative Examples 12-22 to prepare the samples.

[0205] [Table 1]

[0206]

[0207] [Table 2]

[0208]

[0209] [Table 3]

[0210]

[0211] [Table 4]

[0212]

[0213] [Table 5]

[0214]

[0215] [Table 6]

[0216]

[0217] [Table 7]

[0218]

[0219] [Table 8]

[0220]

[0221] As shown in Table 1, by contacting a surface treatment agent containing a specified hydrosilane compound and a borane catalyst with a polyolefin-containing molded article having polar groups on its surface in a solvent containing 10% by volume or more of a hydrocarbon solvent having at least one substituent and a total carbon number of 5 or more, a dehydrogenation condensation reaction is carried out between the molded article and the hydrosilane compound, thereby enabling surface modification without excessively corroding the surface of the polyolefin-containing molded article.

[0222] On the other hand, in comparative examples using solvents that do not meet the requirements, the molded articles containing polyolefins either dissolve or cannot be surface-modified, indicating that it is impossible to manufacture the desired surface-modified molded articles.

[0223] Industrial availability

[0224] According to the present invention, a surface treatment agent can be provided that can perform surface modification without excessively eroding the surface of molded articles containing polyolefins.

[0225] According to the present invention, a surface treatment agent kit can be provided that enables surface modification without excessively eroding the surface of molded articles containing polyolefins.

[0226] According to the present invention, it is possible to provide a surface-modified molded article comprising a polyolefin.

[0227] According to the present invention, a method for manufacturing a surface-modified molded article is provided, which enables surface modification without excessively eroding the surface of the molded article containing polyolefin.

Claims

1. A surface treatment agent comprising a hydrosilane compound and a borane catalyst, said hydrosilane compound having Si-H groups on silicon atoms bonded to them in molecular structure A. The surface treatment agent is used to modify a polyolefin-containing molded article having polar groups on its surface. The molded article is contacted in a solvent containing 10% by volume or more of a hydrocarbon solvent having at least 5 carbon atoms with at least one substituent, thereby causing a dehydrogenation condensation reaction between the molded article and the hydrosilane compound, thereby modifying the molded article through the molecular structure A.

2. The surface treatment agent according to claim 1, wherein, The at least one substituent of the hydrocarbon solvent is methyl.

3. The surface treatment agent according to claim 1 or 2, wherein, The polyolefin is a cyclic olefin (co)polymer.

4. A surface treatment agent kit comprising agent A containing a hydrosilane compound and agent B containing a borane catalyst, said hydrosilane compound having Si-H groups with hydrogen atoms bonded to silicon atoms in molecular structure A. Agent A and Agent B each contain at least one organic solvent, which may be the same or different. At least 10% by volume of the total organic solvent in Agent A and Agent B is a hydrocarbon solvent having at least one substituent and a total carbon number of 5 or more. The surface treatment agent kit is used to modify the surface of a polyolefin-containing molded article with polar groups on its surface. By contacting the molded article with agent A and agent B, a dehydrogenation condensation reaction is carried out between the molded article and the hydrosilane compound, thereby modifying the surface of the molded article through the molecular structure A.

5. The surface treatment agent kit according to claim 4, wherein, The at least one substituent of the hydrocarbon solvent is methyl.

6. The surface treatment agent kit according to claim 4 or 5, wherein, The polyolefin is a cyclic olefin (co)polymer.

7. A surface-modified molded article comprising a polyolefin having a molecular structure A on its surface, in, R 1 R 2 Y 1 Y 2 Y 3 Y 4 Each of the following independently represents a hydrogen atom, a straight-chain or branched alkyl group having 1 to 30 carbon atoms, and -OR 4 R 4 R represents a straight-chain or branched alkyl group having 1 to 30 carbon atoms. 1 R 2 R 4 Y 1 Y 2 Y 3 Y 4 Alkyl groups with 1 to 30 carbon atoms, whether straight-chain or branched, can have fluorine atoms as substituents, and multiple carbon atoms can be replaced by oxygen atoms. However, there are no cases where oxygen atoms are substituted in more than two consecutive forms. 1 X 2 X 3 Each can be independently represented as -O- or a single bond, where l represents an integer greater than 1 and less than 300, and n and m represent integers greater than 0 and less than 300. Where R... 1 R 2 Y 1 Y 2 Y 3 Y 4 At least one of them is not a hydrogen atom.

8. The surface-modified molded article according to claim 7, wherein, The surface-modified molded articles are used for medical purposes and are shaped as petri dishes, tubes, well plates, syringes, or pipette tips.

9. The surface-modified molded article according to claim 7 or 8, wherein, The polyolefin is a cyclic olefin (co)polymer.

10. A method for manufacturing a surface-modified molded article, the method comprising the following steps: In solvents containing 10% by volume or more of a hydrocarbon solvent having at least one substituent and a total carbon number of 5 or more, In the presence of a borane catalyst, a molded article formed of polyolefin with polar groups on its surface is brought into contact with a hydrosilane compound having Si-H groups bonded to silicon atoms in molecular structure A. The molded article is subjected to a dehydrogenation condensation reaction with the hydrosilane compound to form the molded article with the surface modified by the molecular structure A.

11. The manufacturing method according to claim 10, wherein, The polar group includes either or both of hydroxyl and carbonyl groups.

12. The manufacturing method according to claim 11, wherein, The polar group is a hydroxyl group.

13. The method for manufacturing a molded article according to claim 10, wherein, The catalyst is tris(pentafluorophenyl)borane.

14. The manufacturing method according to claim 10, wherein, The surface-modified molded article is a molded article for medical use, and the surface-modified molded article is a petri dish, tube, well plate, syringe or pipette tip.

15. The manufacturing method according to claim 10, wherein, The at least one substituent of the hydrocarbon solvent is methyl.

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